THE  HYDROGENATION 
OF  OILS 

CATALYZERS  AND  CATALYSIS 

AND 

THE   GENERATION   OF   HYDROGEN 


BY 

CARLETON   ELLIS,    S.  B. 

Member  of  American  Chemical  Society,  American  Institute  of  Chemical 

Engineers.  American  Electrochemical  Society,  American  Wood 

Preservers  Association,  Franklin  Institute,  Inventors 

Guild,  Society  of  Chemical  Industry  (London) 

and  German  Chemical  Society  (Berlin) 


14=5  ILLUSTRATIONS 


NEW   YORK 

D.  VAN   NOSTRAND   COMPANY 
25  PARK  PLACE 

1914 


COPYRIGHT,  1914, 

BY 
D.  VAN  NOSTRAND  COMPANY 


Stanbopc  ftress 

F.    H.GILSON   COMPANY 
BOSTON,  U.S.A. 


PREFACE 


THE  course  of  development  of  the  oil  industry  is  marked  by  the 
milestones  of  discovery,  embracing  glycerine  recovery,  hydrolytic 
saponification,  the  Twitchell  process,  the  distillation  of  fatty  acids,  the 
Wesson  process  of  oil  deodorization,  the  pioneer  work  of  Mege  Mouries 
and  the  resulting  margarine  industry,  the  intimate  incorporation  of 
oil  and  stearin  by  sudden  chilling  to  form  lard  compound,  the  de- 
sulfurization  of  petroleum  oils  by  copper  oxide;  and  to  the  foregoing 
should  be  added  a  comparatively  recent  discovery,  the  technical 
hydrogenation  of  oils,  which  is  destined  to  take  a  very  prominent 
place  in  the  oil  industry.  The  extensive  use  of  the  hydrogenation  proc- 
ess is  beyond  doubt;  it  must  in  fact  be  regarded  as  the  most  important 
advance^  in  the  technology  of  oils  during  recent  years.  The  probable 
effect  on  the  oil  and  allied  industries  and  on  the  oil  and  oil  seed  markets 
is  difficult  to  forecast,  as  the  full  possibilities  of  the  process  cannot  yet 
be  determined. 

The  whole  structure  of  hydrogenation  resides  in  the  catalytic  action 
of  practically  only  a  limited  number  of  metals  and  their  compounds, 
which  awaken  the  usually  passive  element  hydrogen  from  its  dormant 
condition  and  thus  enable  its  combination  with  unsaturated  bodies. 
Often  the  term  catalysis  is  said  to  be  an  overworked  expression  under 
cover  of  which  chemists  may  find  refuge  when  pressed  for  an  explana- 
tion of  obscure  phenomena.  But  whether  or  not  the  term  is  over- 
worked it  is  indeed  certain  that  with  rational  treatment  catalyzers 
are  the  hardest  workers  in  the  domain  of  chemistry  and  may  effect 
the  transformation  of  a  prodigious  amount  of  raw  material  without 
detriment  to  themselves  unless  perchance  their  labors  are  checked  by 
the  accidental  presence  of  certain  unfriendly  bodies  or  catalyzer 
"  poisons  "  as  these  are  termed. 

In  1823  Dobereiner  found  that  hydrogen  would  ignite,  when,  in  the 
presence  of  air,  it  was  exposed  to  finely-divided  platinum,  and  this 
manifestation  of  catalytic  activity  by  platinum  and  also  palladium 
was  studied  during  the  middle  of  the  last  century  by  Liebig,  Debus 
and  others.  In  1888  Mond  made  use  of  reduced  nickel  on  a  porous 
carrier,  curiously  enough  not  to  add  hydrogen  but  to  eliminate  it, 
thus  providing  a  method  of  preparing  hydrogen  gas.  Ten  years  or 

iii 


SOOO^O 


iv  PREFACE 

so  later,  Sabatier  and  Senderens  reversed  this  procedure  and  made 
such  nickel  carry  hydrogen  to  unsaturated  organic  compounds  of  a 
character  which  could  be  vaporized  readily.  Then  in  1903  came  Nor- 
mann  who  disclosed  the  application  of  nickel  catalyzer  to  the  hydro- 
genation  of  fixed  or  fatty  oils  or  the  production  of  stearin  from  olein. 
But  it  was  years  afterwards  before  the  idiosyncrasies  of  catalytic 
nickel  were  fully  understood  and  the  technical  difficulties  of  hydro- 
genation  were  surmounted  so  as  to  afford  eminently  practical  results. 

To-day  this  branch  of  the  oil  industry  is  growing  by  leaps  and 
bounds  and  its  advent  into  the  field  has  brought  a  flood  of  congratu- 
lations, protests  and  criticisms,  market  disturbances,  and  great  activity 
among  chemists  to  improve  the  catalytic  materials  and  processes  of 
treatment  involved. 

The  present  book.it  is  hoped  will  be  of  assistance  to  the  practical 
worker  as  well  as  to  the  student  of  oils  and  fats.  It  has  been  the  out- 
growth of  a  number  of  years  of  observation  and  experience  involving 
the  collection  of  a  considerable  amount  of  data  from  many  sources. 
An  attempt  was  made  by  the  author  to  present  the  matter  in  brief  form 
before  the  Society  of  Chemical  Industry  in  1912  and  the  present 
volume  is  based  on  the  general  plan  or  arrangement  of  material  adopted 
in  that  paper. 

Heretofore,  the  literature  on  hydrogenation  has  been  scattered 
through  many  periodicals  and  no  effort  has  been  made  to  collect  this 
material  and  arrange  it  in  book  form,  although  the  treatises  of  Hefter 
and  Ubbelohde  and  Goldschmidt  include  a  few  pages  on  the  conversion 
of  soft  fats  by  various  methods  to  stearic  acid  or  stearin;  but  such 
reviews  have  been  too  brief  to  afford  the  practical  operator  sufficient 
working  material. 

A  considerable  mass  of  data  including  practically  all  that  has  been 
advanced  on  the  subject  of  hydrogenation  of  fatty  oils  has  been  col- 
lected and  arranged  in  this  volume.  The  observations  and  opinions 
of  many  minds  have  been  brought  together.  Some  of  these  views 
obviously  are  sound,  others  are  open  to  grave  doubt  and  still  others 
are  of  a  contradictory  or  polemical  nature.  Whether  or  not  in  the 
treatment  of  this  material  to  carry  through  a  vein  of  critical  comment 
was  a  problem  which  confronted  the  author  and  the  conclusion  was 
reached  that  at  this  stage  of  a  young  art,  it  would  be  inadvisable  in 
general  to  do  more  than  array  the  multitude  of  processes,  formulae 
proposals  and  opinions,  leaving  to  the  reader  the  selection  of  that 
which  should  prove  of  greatest  utility. 

A  few  years  hence  when  oil  hydrogenation  will  have  found  its 
measure  and  the  more  important  points  concerning  it  have  reached 


PREFACE  v 

definite  settlement,  the  allotment  of  space  to  a  number  of  the  discus- 
sions appearing  on  the  following  pages  would  hardly  be  warranted,  but 
at  the  present  time  when  many  are  desirous  of  having  at  hand  a  treatise 
which  comprises  all  or  nearly  all  the  published  work  to  date,  containing 
though  it  does  a  considerable  divergency  of  opinion,  there  appears 
ample  justification  for  the  inclusion  of  material  which  later  may  be 
considered  superfluous. 

Frequent  reference  has  been  made  to  the  material  scattered  through 
the  literature  and  acknowledgment  is  rendered  to  these  sources  of 
information,  especially  to  the  Journal  of  the  Society  of  Chemical 
Industry  and  the  Seifenseider  Zeitung. 

C.  E. 

MONTCLAIR,  N.  J. 

June  15,  1914. 


CONTENTS 


PAGES 

CHAPTER  I.  —  METHODS  OF  HYDROGENATION 1-32 

Attempts  to  Hydrogenate  Oleic  Acid  —  A  Review  of  the  Art  — 
Work  of  Lewkowitsch  —  Goldschmidt  —  de  Wilde  and  Reychler  — 
Chlorination  of  Oils  —  Imbert,  Ziirrer  —  Tissier  —  Freimdlich  and 
Rosauer  —  Varentrapp  Reaction  —  Schmidt  Zinc  Chloride  Process  — 
Processes  Involving  the  Aid  of  Electricity  —  Magnier,  Bragnier  and 
Tissier,  Hemptinne,  Petersen,  Bohringer  and  Bruno  Waser — Hydrogen- 
ation  by  Catalytic  Action  —  Kolbe,  Sayteff,  Sabatier  and  Senderens — 
Nickel  Catalyzer  —  Leprince  and  Siveke  and  the  Normann  Patent  — 
Hydrocarbon  Oils —  Day  —  Oleic  Acid  Treated  in  the  Form  of  Vapor — 
Schwoerer,  Bedford  —  Erdmann  System  —  Vereinigte  Chemische 
Werke  A.G.  —  Kayser  Apparatus  —  Testrup  and  Wilbuschewitsch  — 
Bedford  and  Williams—  Nickel  Oxide — Nickel  Carbonyl— Shukoff  - 
Day,  Phillips  and  Bulteel  —  Schlinck  Centrifugal  Apparatus  — 
Ellis  System  —  Speed  of  Catalytic  Action  —  The  Treatment  of  Oleic 
Acid  —  Connstein  and  von  Schonthan,  Pf  eilring  Reagent  —  De  Hemp- 
tinned 

CHAPTER  II.  —  METHODS  OF  HYDROGENATION  (Continued) 33-49 

Utescher  —  Action  of  Light  —  Walter's  Method  —  Birkeland 
and  Devik  —  Brochet  —  de  Kadt  —  Markel  and  Crosfield  —  Tem- 
perature of  Hydrogenation  —  Caro  —  Fuchs  —  Nickel  Carbonyl, 
Lessing  —  Kamps  —  Bremen  Besigheimer  Olfabriken  —  Sherieble  — 
The  Calvert  System  —  Wilbuschewitsch  Apparatus  —  Wimmer  and 
Higgins  —  Ellis  —  Bock. 

CHAPTER  III.  —  CATALYZERS  AND  THEIR  ROLE  IN  HYDROGENATION 

PROCESSES.     THE  BASE  METALS  AS  CATALYZERS 50-59 

Nickel  Catalyzers  —  Preparation  —  Bodies  Acting  as  Poisons 
for  Catalytic  Nickel  —  Use  of  Nickel  by  Mond  —  Sabatier  and  Sender- 
ens  —  Behavior  of  Catalytic  Nickel  —  Senderens  and  Aboulenc  — 
Nickel  Obtained  by  Reducing  Various  Oxides  —  Classification  of 
Catalyzers. 

CHAPTER  IV.  —  THE  BASE  METALS  AS  CATALYZERS 60-87 

Nickel  Oxide  —  Bedford  and  Williams  —  Erdmann  —  Sabatier 
and  Espil  —  Relative  Efficiency  of  Nickel  and  its  Oxide  —  Meigen 
and  Bartels  —  Kast  —  de  Kadt  —  Nickel  Soaps  —  Hausmann  — 
Wimmer  and  Higgins  —  Nickel  Formate  —  Crosfield  —  Kayser  — 
Wilbuschewitch  —  Frank  —  Eldred  —  Miiller  —  Nickel  Hypophos- 
phite  —  Bremen  Besigheimer  Olfabriken  —  Flaky  Nickel  —  Hage- 
mann  and  Baskerville — Boberg — Boron  as  a  Catalyzer — Hildeshei- 
mer  —  Continuous  Process  for  the  Reduction  of  Nickel  Oxide. 


viii  CONTENTS 

PAGES 

CHAPTER  V.  —  NICKEL  CARBONYL 88-97 

Discovery  of  Nickel  Carbonyl  by  Mond  —  Properties  —  Manu- 
facture on  the  Large  Scale  —  Langer  —  Dewar  —  Catalytic  Action 
of  Nickel  Derived  from  Nickel  Carbonyl. 

CHAPTER  VI.  —  THE  RARE  METALS  AS  CATALYZERS 98-110 

Palladium  —  Fokin's  Experiments  —  The  Work  of  Paal  —  Pal- 
ladium Chloride  —  Skita  —  Colloidal  Platinum  and  Palladium  — 
Karl  —  Paal  and  Windisch  —  Osmium  Oxides  —  Lehmann  —  Thron 

—  Porter  —  Schick  —  Perl  —  Monroe  —  Paal  and  Amberger. 

CHAPTER  VII.  —  THE  OCCLUSION  OF  HYDROGEN  AND  THE  MECHANISM 

OF  HYDROGEN  ADDITION 111-122 

Absorption  of  Hydrogen  by  Various  Metals  —  Sieverts  and 
Krumhaar  —  Dehydrogenation  —  Padoa  and  Fabris  —  Palladium 
Hydrides  —  Wieland  —  Nickel  Hydrides  —  Sabatier  —  Maver  and 
Altmayer  —  Phenomena  of  Adsorption  —  McBain  —  Reducing  Power 
of  Hydrogen  —  Tomassi  —  Occlusion  of  Hydrogen  by  Charcoal  — 
Titoff  —  Firth  —  Electrolytic  Hydrogen  —  Fokin. 

CHAPTER  VIII.  —  THE  ANALYTICAL  CONSTANTS  OF  HYDROGENATED 

OILS 123-139 

Changes  in  Specific  Gravity,  Melting  Point  and  Iodine  Number 

—  Normann    and    Hugel  —  Index    of    Refraction  —  Saponification 
Value  —  Cholesterol    and   Phytosterol  —  Bonier  —  Willstatter    and 
Mayer  —  The  Unsaponifiable  Constituents  of  Hydrogenated  Oils  — 
Marcusson  and  Meyerheim  —  Hardened  Castor  Oil  —  Garth  —  Bou- 
douin  Reaction,  Halphen  and  Becchi  Tests  —  Erucic  Acid  —  Lew- 
kowitsch  —  Majima  and  Okada  —  Hardened    Peanut  Oil  —  Kreiss 
and  Roth  —  Observations  of  Knapp  —  The  Investigations  of  Bonier 

—  Leimdorfer  —  Color    Reactions    of    Hydrogenated    Fish    Oils  — 
Grimme  —  Codex  Alimentarius  Austriacus  —  Aufrecht  —  Tests  for 
Nickel  —  Dimethylglyoxime  —  Tchugaeff  —  Fortini  —  Benzildiox- 
ime  —  Atack  —  Colorimetric    Method  —  Lindt  —  The    "  Hydrogen 
Value"— Fokin. 

CHAPTER  IX.  —  EDIBLE  HYDROGENATED  OILS 140-158 

Lard  Compound  Manufacture  —  Advantages  in  the  Use  of 
Hydrogenated  Oil  —  Edibility  of  Hydrogenated  Oils  —  Effect  of 
Nickel  in  the  Hardened  Product  —  Bomer  —  Normann  and  Hugel  — 
Meyerheim  —  Hardened  Whale  Oil  in  Fats  Intended  for  Edible 
Purposes  —  Bohm,  Lieber  and  Keutgen  —  Miscellaneous  Hardened 
Oil  Products  —  Ellis  —  Deveraux  —  Boyce  —  Wilbuschewitsch. 

CHAPTER  X.  —  USES  OF  HYDROGENATED  OILS  AND  THEIR  UTILIZA- 
TION IN  SOAP  MAKING 159-190 

Applications  of  Hardened  Oils  —  Fish  Oil  —  Tsujimoto  —  Whale 
Oil  —  Garth  —  Products  of  the  Germania  Olwerke  —  The  Investi- 
gations of  Schaal  on  the  Uses  of  Hydrogenated  Oils  in  the  Manu- 


CONTENTS  ix 

PAGES 

facture  of  Soap  —  Bergo  —  Limitations  on  the  Use  of  Hydrogenated 
Oil  —  Hauser  —  Ribot  —  Weber  —  Miiiler  —  Fatty  Acids  of  Hydro- 
genated Oils  —  Hajek  —  Garth  —  Tariff  Ratings  —  Bohra  —  Cru- 
tolin  Soaps  —  Hydrogenated  Linseed  Oil  and  Soaps  Made  from  It  — 
Linolith. 

CHAPTER  XI.  —  HYDROGENATION  PRACTICE 191-194 

Catalyzer  Apparatus  —  Hydrogenation  Plant  —  Precautions  to 
be  Observed. 

CHAPTER  XII.  —  THE  HYDROGEN  PROBLEM  IN  OIL  HARDENING 195-199 

Hydrogen  Requirements  of  Oils  —  Sources  of  Hydrogen  —  By- 
Product  Hydrogen  —  Water  Gas  —  Coke  Oven  Gas  —  Walter's  Con- 
clusions. 

CHAPTER  XIII.  —  WATER  GAS  AS  A  SOURCE  OF  HYDROGEN  AND  THE 

REPLACEMENT  OF  CARBON  MONOXIDE  BY  HYDROGEN 200-207 

Reaction  of  Carbon  Monoxide  with  Lime  in  the  Presence  of 
Steam  —  Engels — Tessie  du  Motay — Chem.  Fabrik  Griesheim  Elek- 
tron  —  Merz  and  Weith  —  Jermanowski  —  Hembert  and  Henry 
Process  —  Mond  and  Langer  —  Elworthy  —  Ellis  and  Eldred  — 
Dieffenbach  and  Moldenhauer  —  Naher  and  Miiiler  —  Pullman  — 
Miscellaneous  Processes  Involving  Interaction  between  Carbon  Mon- 
oxide and  Steam. 

CHAPTER  XIV.  —  LIQUEFACTION  AND  OTHER  METHODS  FOR  THE  RE- 
MOVAL OF  CARBON  DIOXIDE 208-216 

Principle  of  Liquefaction  by  Compression  —  Hitdebrandt  — 
Linde  System  —  Liquefaction  Apparatus  —  Claude  —  Jouve  and 
Gautier  —  Vignon  —  Absorption  of  Carbon  Monoxide  by  Chemical 
Agents  —  Frank  Process. 

CHAPTER    XV.  —  HYDROGEN    BY    THE    DECOMPOSITION    OF    HYDRO- 
CARBONS      21 7-224 

Effect  of  Heat  on  Hydrocarbons  —  Acetylene  —  Pictet  —  Car- 
bonium  Company  —  Wachtolf  —  Geisenberger  —  Decomposition  of 
Oils  —  Rincker  and  Wolter  System  —  Oechelhauser. 

CHAPTER  XVI.  —  HYDROGEN  BY  THE  ACTION  OF  STEAM  ON  HEATED 

METALS 225-242 

Reaction  of  Steam  with  Iron  —  Giffard  —  Lewes  Process  — 
Dellwik-Fleischer  System  —  Lane  Process  —  Processes  Devised  by 
Messerschmitt  -  -  Elworthy  —  Internationale  Wasserstoff-Aktien- 
Gesellschaft  —  Strache  System  —  Dieffenbach  and  Moldenhauer  — 
Badische  Co.  —  Belou  —  Vignon's  Apparatus  —  Effect  of  Passing 
Steam  through  Molten  Metal  —  Gerhartz  —  Jaubert  Method  —  Ac- 
celeration of  the  Reaction  by  Catalytic  Agents  —  Saubermann  — 
Gautier  and  Clausmann. 

CHAPTER  XVII.  —  ACTION  OF  ACIDS  ON  METALS 243-245 

Cost  of  Generation  —  By-Products  —  Barton  System  —  Method 
Used  by  Pratis  and  Marengo  —  Proposal  of  Bruno. 


X  CONTENTS 

PAGES 

CHAPTER  XVIII.  —  MISCELLANEOUS  METHODS  OF  HYDROGEN  GEN- 
ERATION   246-256 

Foesterling  and  Philipp  —  Brindley  —  Calcium  Hydride  —  Jau- 
bert  —  Bamberger,  Bock  and  Wanz  —  Reaction  between  Zinc  Dust 
and  Calcium  Hydrate  —  Schwartz  —  The  Hydrogenit  Process  —  Jau- 
bert  —  The  Silicol  Process  —  The  Hydrik  Process  —  Mauricheau- 
Beaupre  —  Chem.  Fab.  Greisheim  Elektron  —  Uyeno  —  Majert  atid 
Richter  System  —  The  Lahousse  Barium  Sulfide  Process  —  The  Ber- 
gius  High-pressure  System. 

CHAPTER  XIX.  —  HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 257-291 

Principles  Involved  in  Generating  Hydrogen  by  Electrolysis  — 
Work  of  D' Arsonval,  Latchinoff  and  Renard  —  Schmidt  Multiple- 
cell  Apparatus  —  Shriver  Oxy-hydrogen  Generator  —  Schoop  Sys- 
tem —  Principle  of  the  Garuti  Generator  —  Types  of  Garuti  Appara- 
tus—  Siemens  and  Obach  Cell  —  Fischer,  Luening  and  Collins  — 
The  Schuckert  System  —  Principle  of  the  Schuckert  Cell  —  Installa- 
tion and  Operating  Features  —  Rotary  Apparatus  Devised  by  Aigner 

—  Cowper-Coles —  Miscellaneous  Forms  of  the  Multiple-cell  Generator 

—  Tommasini    Cell  —  Vareille    Apparatus  —  The   Burdett    System 
—  The  System  of  the  International  Oxygen  Co. 

CHAPTER  XX.  —  SAFETY  DEVICES 292-300 

Davy  Wire  Gauze  —  Glass  Wool  —  Boynton's  Device  —  Steel 
Wool  —  Ohmann  —  Explosions  When  Compressing  —  Bramkamp  — 
Lelarge  —  Summary  of  Methods  of  Making  and  Handling  Hydrogen 

—  Purification  of  Hydrogen  —  Badische  Co.  —  Renard  —  Wenzki  — 
Rabenalt  —  Knowles  System  —  Frank  Process. 

APPENDIX 301-325 

Hydrogenated  Oil  Patent  Litigation. 

INDEX  .  327-340 


THE  HYDROGENATION  OF  OILS 


CHAPTER  I 
METHODS   OF   HYDROGENATION 

FOR  years  the  dream  of  the  oil  chemist  was  to  find  a  solution  to  the 
problem  of  converting  oleic  acid  into  stearic  acid,  or  olein  into  stearin, 
simply  by  the  addition  of  hydrogen,  so  as  to  make  valuable  hard  fats 
from  relatively  cheap  raw  material.  Superficially  the  problem  looked 
simple.  Oleic  acid<is  the  next  door  neighbor  of  stearic  acid,  apparently 
differing  only  in  having  a  little  less  hydrogen  than  stearic  acid  has  in 
its  constitution.  Only  a  trifling  amount  of  hydrogen,  less  than  one 
per  cent,  is  required  to  transform  oleic  into  stearic  acid. 

But  the  problem  was  far  from  simple  as  oleic  acid  stubbornly  resisted 
the  invasion  of  hydrogen  into  its  structure  to  any  material  extent  under 
the  earlier  methods  of  hydrogen  addition,  and  not  until  recent  years, 
with  the  discovery  of  effective  hydrogen  carriers  or  catalyzers,  has  it 
become  possible  to  bring  about  this  conversion  economically  with  large 
yields  so  as  to  warrant  commercial  exploitation  in  an  extensive  way. 

Now  the  problem  is  solved,  and  in  different  parts  of  the  globe  dozens 
of  plants  turning  out  daily  enormous  quantities  of  "  hardened  oil  "  pre- 
pared by  the  treatment  of  vegetable  or  other  oil  with  hydrogen  have 
been  established.*  So  eagerly  has  the  oil  handling  world  lent  itself  to 
the  idea  that  already  the  stearin  market  has  lost  its  firmness  and  much 
speculation  is  rampant  as  to  the  nature  of  price  readjustments  which 
perhaps  are  on  the  way.  Unquestionably  hydrogenated  or  hardened 
oil  has  taken  its  place  in  the  oil  market  as  a  staple  product. 

A  REVIEW  OF  THE  ART.ft 

Many  attempts  to  hydrogenate  oleic  acid  have  been  made.  Re- 
viewing this  subject  in  1897  §  Lewkowitsch  refers  to  the  ease  with 

*  A  list  of  over  twenty  firms  in  different  parts  of  the  world  having  plants  for 
hardening  oils  is  found  in  Seifensieder  Zeitung,  1914,  349. 

t  See  Ellis,  J.  S.  C.  I.,  1912,  1155;  J.  Ind.  Eng.  Chem.,  1913,  95;  The  American 
Perfumer,  1913. 

t  The  production  of  stearic  acid  and  other  acids  or  products  of  high  melting  point 
from  oleic  acid  is  discussed  by  Hefter,  Technologic  der  Fette  und  Ole,  Vol.  Ill, 
795  and  994;  also  by  Ubbelohde  und  Goldschmidt,  Handbuch  der  Chemie  und 
Technologic  der  Ole  und  Fette,  Vol.  Ill,  152. 

§  J.  S.  C.  I.,  389  (1897). 

1 


2  THE  HYDROGENATION  OF  OILS 

which  the  lower  members  of  the  oleic  series  are  converted  into  satu- 
rated acids  and  states  that  "  oleic  acid  itself  resists  all  attempts  at 
hydrogenization,"  further  remarking  that  he  had  "  carried  out  a  large 
number  of  experiments  in  this  direction  under  most  varied  conditions, 
but  hitherto  all  of  these  gave  negative  results." 

Prior  to  this,  however,  Goldschmidt,  in  1875,*  had  reduced  oleic 
acid  by  means  of  hydriodic  acid  and  amorphous  phosphorus  at 
200°  to  210°  C.  This  presumably  led  to  the  attempted  commercial 
development  of  a  process  by  de  Wilde  and  Reychlerf  involving  heating 
oleic  acid  to  280°  C.  with  1  per  cent  of  iodine,  adding  and  melting 
therein  a  certain  quantity  of  tallow  soap,  and  then  boiling  with  acidu- 
lated water.  The  product  was  then  distilled  and  the  iodine,  in  part, 
recovered  from  the  pitch.  The  yield  of  stearic  acid  or  saturated  fat 
is  stated  to  be  approximately  70  per  cent  of  the  theoretical.  Only 
about  two-thirds  of  the  iodine  could  be  recovered  so  the  process  appar- 
ently did  not  find  technical  use.J  Should  the  much  lauded  method 
of  treating  kelp,  primarily  for  obtaining  potash  salts,  come  into  use,  a 
cheap  supply  of  iodine  would  be  available  which  might  then  make  the 
Wilde  and  Reychler  process  of  some  technical  interest. 

Chlorine  in  lieu  of  iodine  has  been  tried,  but  great  difficulty  has  been 
experienced  in  securing  an  autoclave  of  resistant  material.  Imbert  § 
recommends  using  quantities  of  chlorine  and  alkali  exactly  calculated 
on  the  iodine  number  of  the  fatty  acid  and  operating  at  a  temperature 
of  120°  to  150°  C.  and  a  pressure  of  about  five  atmospheres  for  a  period 
of  six  hours. 

Zurrer  ||  chlorinates  the  fatty  acid  and  then  heats  with  water  in  the 
presence  of  a  finely-divided  metal,  as  zinc  or  iron.  Lewkowitsch  alleges 
that  the  treatment  of  monochlor-stearic  acid  in  this  manner  causes  a 
reversion  to  oleic  acid. 

Tissier,  in  1897,  If  lays  claim  to  a  process  for  the  reduction  of  oleic 
acid  by  nascent  hydrogen.  Powdered  metallic  zinc  is  placed  in  an  auto- 
clave, water  and  the  fatty  material  containing  olein  being  introduced, 
and  treated  under  pressure. 

Under  the  circumstances  the  glyceride  is  hydrolyzed  to  fatty  acid 
and  glycerine,  and  according  to  Tissier  nascent  hydrogen  is  evolved  by 

*  Sitz.  b.  d.  Wiener  Akad.  d.  Wiss.,  72,  366. 
t  Bull.  Soc.  Chim.  [3],  1,  295  (1889). 
t  Chem.  Ztg.,  1889,  595. 

§  U.  S.  Patent  No.  901,905,  October  20,  1908;  see  also  Bull.  Soc.  Chim.,  1899, 
695,  707. 

II   German  Patent  No.  62,407,  August  8,  1891. 
1f  French  Patent  No.  263,158,  January  16,  1897. 


METHODS  OF  HYDROGENATION  3 

virtue  of  the  finely-divided  metal  and  reduces  the  oleic  to  stearic  acid. 
Freundlich  and  Rosauer  *  claim  the  Tissier  process  to  be  inoperative. 

The  conversion  of  oleic  acid  into  palmitic  and  acetic  acids  by  means 
of  caustic  potash  in  accordance  with  the  Varentrapp  reaction  f  has  not 
proved  to  be  of  much  commercial  significance,  although  it  appears 
that  certain  firms  have  been  making  use  of  the  process  in  a  limited  way. 

The  Schmidt  zinc  chloride  process}:  involves  heating  oleic  acid  and 
zinc  chloride  at  exactly  185°  C.  while  interaction  is  taking  place. 
"  Deviation  from  this  point  leads  to  an  increase  of  liquid  substance. 
Unfortunately  the  solid  candle  material  must  be  distilled  and  the  con- 
siderable proportion  of  /3-hydroxy-stearic  acid  (melting  point  82°  C.) 
in  the  crude  product  is  seriously  diminished  by  the  partial  conversion 
of  this  acid  into  oleic  and  iso-oleic  acids.  Thus,  from  a  candle-maker's 
point  of  view,  a  substance  of  high  melting  point  is  rendered  practically 
valueless.  Schmidt's  process  was  tried  on  the  large  scale  in  an  Austrian 
candle  works.  The  quantity  of  liquid  unsaponifiable  substance  ob- 
tained was,  however,  so  large  that  commercial  success  was  out  of  the 
question." 

Many  processes  based  on  the  well-known  action  of  sulfuric  acid  on 
oleic  acid  have  been  proposed.  Hydroxy-stearic  acid  is  obtained  by 
steaming  the  product.  It  would  lead  us  too  far  from  the  present 
subject  to  enter  into  any  further  discussion  of  these  reactions. 


PROCESSES  INVOLVING  APPLICATION  OF  ELECTRICITY 

In  1886  Weineck  §  called  attention  to  the  possibility  of  electrolytic 
addition  of  hydrogen  to  oleic  acid.  Kuess  ||  later  attempted  to  apply 
the  electric  current  in  the  steam  distillation  of  fatty  acids. 

In  patents  taken  out  by  Magnier,  Bragnier  and  Tissier,  1f  the  fatty 
material  is  acidified  with  sulfuric  acid,  whereupon  the  acidified  mass 
is  mixed  with  5  to  6  times  its  weight  of  water  and  then  under  a  pressure 
of  5  atmospheres  is  subjected  to  the  action  of  an  electric  current,  which 
generates  hydrogen  in  a  nascent  state. 

An  interesting  method  of  converting  oleic  into  stearic  acid  is  that 
comprised  in  the  Hemptinne  electric  discharge  process.  The  method 

*  Chem.  Ztg.,  1900,  566. 

t  J.  S.  C.  I.,  98  (1883),  200  (1884). 

I  Lewkowitsch,  "Oils,  Fats  and  Waxes,"  p.  664. 
§  Osterr.  Privil.,  10,  400  (July  19,  1886). 

II  Chem.  Ztg.,  1896,  618. 

f  British  Patent  3363,  1900;  German  Patent  126,446,  October  3,  1899,  and 
additional  German  Patent  132,223. 


4  THE  HYDROGENATION  OF  OILS 

is  carried  out  by  interposing  a  thin  layer  of  the  oil  in  the  path  of  an 
electric  discharge,  while  bringing  hydrogen  into  contact  with  the  oil.* 
Fig.  1  shows  the  arrangement  of  apparatus  for  this  purpose.  The 
conversion  is  effected  in  a  chamber  having  an  inlet  pipe  H,  furnishing 
hydrogen  under  constant  pressure.  Oleic  acid  is  supplied  by  a  pipe 
0  to  a  sprinkling  device  which  discharges  the  acid  onto  a  system  of 
parallel  plates  consisting  of  the  glass  plates  G  and  alternately  the  metal 
plates  M,  N.  The  metal  plates  M  are  connected  to  one  pole,  the 
others,  N,  being  connected  with  the  other  pole  of  a  source  of  electricity. 


E 


H  H  H 

?   J       y   if   ' 


FIG.  1. 


As  the  oil  passes  over  the  plates  the  electrical  discharge  causes  con- 
version of  some  oleic  acid  into  stearic  acid,  and  analogous  compounds 
having  melting  points  in  the  neighborhood  of  69°  C. 

Hemptinne  prefers  to  work  at  pressures  less  than  atmospheric. 
The  yield  is  lower  at  atmospheric  pressure.  By  treatment  in  this 
manner  it  is  not  difficult  to  secure  a  yield  of  20  per  cent  of  stearic  acid. 
Repeated  treatment  permits  even  up  to  about  40  per  cent  yield.  Here, 
as  so  often  elsewhere,  the  effect  of  mass  action  becomes  manifest  and 
as  the  content  of  stearic  acid  increases  the  speed  of  reaction  greatly 
decreases.  Much  better  results  are  obtained  by  saturating  to  the 
extent  of  about  20  per  cent,  removing  the  stearic  acid  by  pressing, 
when  the  oil  of  reduced  stearic  acid  content  is  again  subjected  to  the 
electric  discharge,  and  a  further  20  per  cent  yield  obtained.  The 
oleic  residue  contains  liquid  condensation  products  amounting  to 
about  40  per  cent  of  the  total  weight.  It  is  stated  that  the  presence 
of  these  bodies  does  not  impair  the  market  value  of  what  some  one  has 
termed  "  electrocuted  "  oleic  acid. 


U.  S.  Patent  797,112,  August  15,  1905. 


METHODS  OF  HYDROGENATION  5 

Petersen*  also  endeavored  to  reduce  oleic  acid  to  stearic  acid  by 
allowing  an  electric  current  to  act  between  nickel  electrodes  on  an 
alcoholic  oleic  acid  solution,  slightly  acidulated  with  sulfuric  acid  or 
preferably  with  hydrochloric  acid.  But  the  yield  of  stearic  acid  was 
small,  even  under  the  most  favorable  conditions,  and  did  not  exceed 
15  to  20  per  cent. 

Petersen  also  endeavored  to  reduce  sodium  oleate  in  aqueous  or 
alcoholic  solution  to  the  stearate.  No  satisfactory  results  were 
obtained. 

C.  F.  Bbhringer  and  Sohne  f  obtained  by  the  same  method  much 
better  results  when  using  as  cathodes,  metallic  electrodes,  which  were 
covered  with  a  spongy  layer  of  the  same  metal.  They  recommend  as 
cathodes  platinized  platinum,  and  also  palladium  electrodes  covered 
with  a  spongy  layer  of  palladium-black.  Nickel  electrodes  are  not  as 
effective. 

Bruno  Waser|  states  that  oleic  acid  or  olein  should  be  sulfonated 
and  freed  from  free  sulfuric  acid  before  adding  hydrogen  electrically 
(cathodic  reduction).  As  an  example,  one  equivalent  of  oleic  acid  is 
mixed  with  two  or  three  equivalents  of  95  per  cent  sulfuric  acid,  the 
temperature  not  being  permitted  to  advance  more  than  5  degrees.  The 
mixture  is  allowed  to  stand  24  hours,  is  then  washed  with  ice  cold 
water  and  dissolved  in  boiling  water.  This  solution  serves  as  catho- 
lyte,  a  30  per  cent  sulfuric  solution  being  the  anode  liquid.  A  di- 
aphragm separates  lead  electrodes.  The  temperature  is  maintained 
at  90°  to  100°  C.  with  a  current  density  of  25  to  100  amperes  per 
square  decimeter,  giving  60  to  70  per  cent  conversion  to  stearic  acid. 

HYDROGENATION  BY  CATALYTIC  ACTION 

Kolbe  §  in  1871  states  that  Saytzeff  reduced  nitrobenzol  to  aniline 
by  passing  the  vapors  of  the  former,  mingled  with  hydrogen,  over 
palladium-black. 

About  twenty-five  years  later  Sabatier  and  Senderens  began  their 
classic  study  of  nickel  and  other  metallic  catalyzers. 

The  work  of  Sabatier  and  Senderens  ||  laid  the  foundation  for  the 

*  Z.  Elektrochemie,  1905,  549. 

t  German  Patents  187,788,  189,332,  1906. 

t  German  Patent  247,454,  March  24,  1911,  and  Seifen.  Ztg.,  1912,  661. 

§  J.  prakt.  Chem.  [2],  4,  418  (1871). 

II  Sabatier  and  Senderens  published  the  results  of  their  earlier  work  in  Comp. 
rend.,  132,  210,  566  and  1254.  A  very  complete  description  of  their  investigations 
appears  in  Ann.  de  Chim.  et  de  Phys.,  1905  (8),  4,  319-488.  See  also  Mailhe  Chem. 
Ztg.,  1907  (31),  1083,  1096,  1117/1146  and  1158;  Chem.  Ztg.,  1908  (32),  229  and 


6 


THE  HYDROGENATION  OF  OILS 


present  processes  of  hydrogenation  of  oils.  These  distinguished 
chemists  first  recognized  the  effectiveness  of  nickel  and  certain  other 
metals  as  carriers  of  hydrogen  and  they  elaborated  a  series  of  brilliant 
experiments  extending  over  a  number  of  years,  which  demonstrated 
that  unsaturated  compounds,  that  is,  bodies  lacking  in  hydrogen,  could 
be  saturated  or  given  the  full  quota  of  hydrogen  by  contact  with  this 
gas  in  the  presence  of  a  catalyzer  or  carrier,  such  as  finely-divided 
nickel.  By  their  painstaking  labors  the  reaction  was  shown  to  be  one 
of  general  application. 

Fig.  2  shows  the  apparatus  used  by  these  investigators  in  the  hydro- 
genation of  bodies  capable  of  vaporization.     In  this  apparatus,  1  is 


FIG.  2. 


a  hydrogen  generator;  2  and  3  are  wash  bottles;  4  is  a  vaporizer 
containing  the  substance  to  be  converted  into  a  vapor;  5  is  a  hydro- 
gen chamber  containing  nickel  catalyzer  and  heated  by  an  oil  bath; 
and  6  is  a  condenser. 

While  a  good  deal  of  work  has  been  done  on  the  hydrogenation  of 
fatty  oils,  the  literature  on  the  subject  is  not  very  profuse  and  only 
through  the  patents  which  have  been  issued  can  we  gather  from  any 

244;  Willstatter  and  Mayer,  Ber.,  1908  (41),  2199;  Paal  and  Amberger,  Ber.,  1905 
(38),  1406  and  2414:  Paal  and  Gerum,  Ber.,  1907  (40),  2209;  1908  (41),  813  and 
2273;  1909  (42),  1553;  Paal  and  Hartmann,  Ber.,  1909  (42),  2239;  Paal  and  Roth, 
Ber.,  1908  (41),  2282;  1909  (42),  1541;  Ipatiew,  Ber.,  1902  (35),  1047;  1904  (37), 
2961;  Chem.  Centralbl.,  1906,  II,  86;  Ber.,  1907  (40),  1270  and  1286;  1908  (41), 
991;  1909  (42),  2089,  2092  and  2100;  Ipatiew,  Jakowlew  and  Rakitin,  Ber.,  1908 
(41),  996;  Ipatiew  and  Philipow,  Ber.,  1908  (41),  1001;  Padoa  and  Carughi,  Chem. 
Centralbl.,  1906,  II,  1011. 


METHODS  OF  HYDROGENATION  7 

published  records  much  that  is  enlightening  as  to  some  of  the  techni- 
cal developments  in  this  industry.  The  patents  concerned  with  the 
matter  have,  moreover,  been  subjected  to  a  great  deal  of  scrutiny 
because  of  the  alleged  basic  character  of  certain  of  them.  For  these 
reasons  the  remainder  of  this  chapter  pertains  very  largely  to 
processes  which  have  been  covered  by  patents  *  in  this  country  or 
abroad. f 

A  German  Patent  139,457,  of  July  26,  1901,  to  J.  B.  Senderens,  is 
probably  the  first  patent  record  having  to  do  with  the  reduction  of 
organic  bodies  by  hydrogen  in  the  presence  of  nickel  catalyzers.  This 
patent  is  for  the  production  of  aniline  from  nitrobenzol  and  involves 
passing  the  latter  body  in  the  form  of  a  vapor  over  heated  nickel, 
copper,  cobalt,  iron  or  palladium  in  the  presence  of  hydrogen.  The 
hydrogen  may  be  in  the  pure  state  or  in  the  form  of  water-gas. 

The  first  disclosure  of  the  possibility  of  hydrogenation  of  oils  in  a 
liquid  state  apparently  comes  from  Leprince  and  Siveke. J  In  Eng- 
land a  corresponding  patent  1515,  of  1903,  was  issued  to  Normann  § 
and  the  latter  patent  has  become  widely  known  because  of  its  alleged 
fundamental  character.  || 


*  Sachs  (Zeitsch.  f/angew.  Chem.,  1913,  No.  94,  784)  reports  183  patents  on  oil 
hardening  of  which  there  are  33  German;  22  French;  51  English;  33  United  States; 
9  Belgium;  and  35  in  other  countries. 

f  The  illustrations  immediately  following  are  largely  derived  from  the  drawings  of 
patent  records  or  have  been  prepared  from  written  descriptions.  In  some  cases  all 
details  deemed  unnecessary  in  the  portrayal  of  the  essential  features  of  these  proc- 
esses have  been  omitted.  The  original  records  should,  of  course,  be  consulted  for 
details.  —  Author. 

t  German  Patent  141,029,  August  14,  1902,  Herforder  Maschinenfett  und 
Oelfabrik. 

§  This  English  patent  is  owned  by  a  large  soap  manufacturing  house  in  England 
and  has  been  passed  on  unfavorably  by  the  courts.  See  Appendix. 

II  The  Seifensieder  Zeitung  (1913),  .1272,  states  that  German  Patent  141,029 
(Leprince  and  Siveke)  is  controlling  in  that  country  so  far  as  the  use  of  metallic 
catalyzers  for  oil  hardening  is  concerned,  because  this  patent  makes  the  first  dis- 
closure of  the  hydrogenation  of  bodies  in  the  liquid  state  by  simple  addition  of  a 
catalyzer  and  introduction  of  hydrogen.  According  to  the  same  journal  (1913), 
1195,  the  Bremen-Besigheimer  Olfabriken  in  Bremen  has  a  large  plant  for  the  hydro- 
genation of  fats  and  oils  which  at  one  time  was  not  in  use  because  of  patent  disputes 
between  this  concern  and  the  Germania  Company.  The  Bremen  Company  has 
made  arrangements  with  the  patent  owners  and  is  now  operating  the  Bremen  plant. 
(Seifen.  Ztg.  (1913),  1273.) 

Leprince  and  Siveke  (German  Patent  141,029  was  assigned  on  July  22,  1910, 
to  Joseph  Crosfield  &  Sons,  Ltd.,  of  England  and  was  again  assigned  on  August  9, 
1911,  to  Naamlooze  Venootschaap  Anton  Jurgen's  Fabriken,  Oss  in  Holland.  The 
latter  concern  on  the  10th  of  July,  1911  founded  the  Oelwerke  Germania,  G.  M.  b.  H., 


8  THE  HYDROGENATION  OF  OILS 

at  Emmerich,  on  the  Rhine.  The  plant  is  reported  to  have  been  put  into  operation 
in  the  Spring  of  1912  —  almost  ten  years  after  the  application  for  German  patent 
141,029. 

The  contentions  of  Professor  Erdmann  (Seifen.  Ztg.  (1914),  32)  present  cer- 
tain points  of  interest.  Referring  to  German  Patent  141,029  which  was  applied 
for  in  1902  and  granted  in  1903,  Erdmann  states  that  eight  years  later  —  without 
being  used  regularly  on  a  large  scale  in  Germany  —  the  rights  were  sold  in  England 
to  Crosfield  &  Sons.  The  requirements  for  the  successful  hardening  of  oils  by  the 
use  of  metallic  nickel  as  a  catalyst  are  regarded  as  having  been  here  given  for  the 
first  time. 

The  German  patent  application  B.  62,366,  IV,  12°,  of  Bedford,  Erdmann  and 
Williams  for  hydrogenating  oils  with  the  aid  of  metallic  oxides,  was  entered  on  March 
16,  1911,  together  with  the  English  priority  of  Dec.  20,  1910,  a  time  therefore  when 
the  Germania  Werke  did  not  exist.  In  addition,  it  is  stated,  Bedford  and  his  col- 
leagues immediately  started  in  to  actually  materialize  their  original  discoveries  and 
ideas  on  a  large  scale;  their  experimental  plant  had  been  working  for  a  considerable 
period  and  in  Germany  at  that  time  oils  had  not  been  hardened  on  a  manufacturing 
scale. 

It  is  not  true,  Erdmann  states,  that  the  process  of  German  patent  141,029  was 
the  first  solution  of  the  problem  of  the  direct  addition  of  hydrogen  to  unsaturated 
fatty  bodies.  It  does  not  cover  the  direct  addition  of  hydrogen  —  a  process  for 
the  direct  addition  of  free  hydrogen  by  means  of  a  catalyst  involves  a  contradiction 
of  terms  —  but  aims  at  the  indirect  addition  to  an  unsaturated  fatty  substance 
by  means  of  a  catalytic  hydrogen  carrier  in  just  the  same  way  as  this  had  already 
been  accomplished  previously  by  Karl  Peters  (Monatshefte  f.  Chemie,  1886  [7],  552), 
and  Reformatoky  (J.  prakt.  Chemie  N.  S.,  1890  [41],  437)  in  the  hydrogenation  of 
oleic  acid  to  stearic  acid  by  the  use  of  iodine  as  the  hydrogen  carrier. 

At  the  time  of  the  application  for  German  patent  141,029  —  that  is,  in  1902  — 
Erdmann  observes  that  the  transformation  of  unsaturated  compounds  contained  in 
liquids  to  saturated  compounds  by  means  of  the  introduction  of  free  hydrogen  into 
the  liquid  with  the  aid  of  a  catalyst  was  not  entirely  unknown.  For  example,  in  1873, 
Saytzeff  (in  Kolbe's  laboratory)  obtained  aminophenol  and  methylamin  by  the  in- 
troduction of  free  hydrogen  into  a  solution  of  nitrophenol  or  nitromethane  in  the 
presence  of  finely-divided  palladium.  (See  J.  prakt.  Chemie.  N.  S.  [6],  128.)  In 
practically  the  same  way,  oleic  acid  could  be  changed  to  stearic  acid  as  Fokin  later 
showed  (Chem.  Centralbl.  (1907),  II,  1324).  Hence  Erdmann  claims  it  is  not  true 
that  the  existence  of  the  discovery  represented  by  German  patent  141,029  can  be 
looked  upon  as  the  first  time  that  a  means  was  found  to  saturate  unsaturated  sub- 
stances in  the  liquid  state  by  means  of  free  hydrogen. 

In  case  any  discovery  can  be  found  set  forth  in  Patent  141,029  —  which  according 
to  the  statements  of  the  English  courts  is  at  least  very  questionable  —  the  new 
idea,  Erdmann  contends,  can  only  be  that  the  two  steps: 

(a)  Hydrogenation  of  liquid  organic  substances  by  the  introduction  of  free  hydro- 
gen in  the  presence  of  a  finely-divided  metallic  catalyst,  and 

(6)  Hydrogenation  of  unsaturated  fatty  substances  in  the  presence  of  a  non- 
metallic  or  not  finely-divided  metallic  catalyst, 

which  steps  were  known  separately,  are  combined  with  one  another  in  this  way, 
that  fatty  substances  are  hydrogenated  by  the  introduction  of  free  hydrogen  in  the 
presence  of  a  finely-divided,  metallic  catalyst,  particularly  nickel  which  was  already 
known  to  be  a  hydrogen  carrier.  Metals,  also,  — for  example  zinc  —  had  been  pro- 


METHODS  OF  HYDROGENATION 


9 


Normann  states  that  he  may  carry  out  the  hydrogenation  of  oils  by 
treatment  either  in  the  form  of  vapors  or  as  liquids.  In  the  former 
case  the  fatty  acid  vapors  together  with  hydrogen  may  be  caused  to 
pass  over  catalytic  material  carried  by  a  pumice  stone  support.  This 
may  be  represented  by  Fig.  3  in  which  A  is  a  bed  containing  granular 
pumice  coated  with  a  metal  catalyzer.  0  is  an  inlet  for  oil  vapors  and 
H  is  an  inlet  for  hydrogen.  The  mixture  passes  through  the  tube  A 
and  the  converted  material  is  withdrawn  at  B.  Normann  notes, 
however,  that  it  is  sufficient  to  expose  the  fat  or  fatty  acid  in  a  liquid 


O 


FIG.  3. 


condition  to  the  action  of  hydrogen  and  the  catalytic  substance.  He 
states  that,  for  instance,  if  fine  nickel  powder  obtained  by  the  reduc- 
tion of  nickel  oxide  in  a  current  of  hydrogen  is  added  to  oleic  acid, 
the  latter  heated  over  an  oil  bath  and  a  strong  current  of  hydrogen 
caused  to  pass  through  it  for  a  considerable  time,  the  oleic  acid  may 
be  completely  converted  into  stearic  acid. 

Fig.  4  shows  very  simple  apparatus,  such  as  might  have  been  used 
by  Normann  to  this  end.  A  is  a  vessel  containing  oil  0  in  which  fine 
particles  of  nickel  are  suspended  while  a  strong  current  of  hydrogen 
from  the  pipe  H  affords  the  hydrogen  requisite  for  reduction  of  the  oil. 
By  this  means  Normann  treated  the  fatty  acid  of  tallow,  having  an 

posed  for  the  hydrogenation  of  oleic  acid  before  1903  (compare  Tissier,  Chem.  Ztg., 
1899  [23],  822). 

Normann  (Seifen.  Ztg.  (1913)^  1381)  regards  the  employment  of  metal  oxides 
or  organic  salts  as  catalyzers  to  fall  within  the  scope  of  the  Leprince  and  Siveke 
(Normann)  German  patent  141,029,  because  of  the  reduction  occurring  when  these 
metallic  compounds  are  exposed  to  hydrogen  in  the  hardening  process.  Meigen  and 
Bartels  (J.  prakt.  Chem.  1914,  290)  support  Normann's  contention.  The  assertions 
of  Erdmann  regarding  the  existence  of  nickel  suboxide  when  hardening  oils  with 
nickel  oxide  catalyzers  are  challenged  by  the  Olwerke  Germania  (Seifen.  Ztg.  1914, 
209)  and  it  is  claimed  that  metallic  nickel  forms  under  the  conditions  to  which  the 
oxide  is  subjected.  In  this  connection,  a  brief  review  of  Ipatieff's  work  is  given. 


10 


THE  HYDROGENATION  OF  OILS 


iodine  number  of  35  and  melting  at  about  46,  thereby  converting  it 
into  a  body  of  improved  color  having  an  iodine  number  of  about  10 
and  a  melting  point  of  about  58.  Normann  also  states  that  commer- 
cial gas  mixtures,  such  as  water-gas,  may 
be  used  in  lieu  of  pure  hydrogen. 

The  disclosures  of  the  Normann  patent 
are,  however,  rather  meagre  and  can  hardly 
be  considered  to  comprehensively  traverse 
the  difficulties  encountered  in  the  practical 
hydrogenation  of  oils  in  a  liquid  state. 

Day  has  brought  out  a  process  *  in  which 
he  treats,  not  fatty  oils,  but  hydrocarbon 
oils,  with  hydrogen  in  the  presence  of  what 
he  terms  a  porous  absorptive  substance 
mentioning  palladium  black,  platinum 
sponge,  zinc  dust,  fuller's  earth  and  other 
clays.  Fig.  5  shows  one  method  proposed  by  Day  to  this  end. 

The  upper  chamber  A  is  filled  with  hydrocarbon  oil,  and  porous  ab- 
sorptive material,  such  as  palladium  black,  is  introduced  into  the  inter- 


A 

I 

FIG.  4. 


FIG.  5. 


FIG.  6. 


mediate  chamber  C  by  way  of  the  plugged  orifice  D.  Any  air  present 
in  C  may  be  expelled  by  flushing  out  with  hydrogen  or  an  indifferent 
gas.  Hydrogen  is  then  admitted  by  the  pipe  H  until  the  porous 

*  U.  S.  Patent  826,089,  July  17,  1906. 


METHODS  OF  HYDRQGENATION  11 

material  has  absorbed  its  full  quota.  The  hydrogen  gas  may  be 
admitted  under  a  pressure  of  100  pounds  or  more  to  the  square  inch. 
When  the  porous  material  in  C  has  become  properly  charged  with 
hydrogen,  the  oil  is  allowed  to  run  from  the  chamber  A  through  the 
chamber  C  into  the  collecting  chamber  E,  hydrogen  being  introduced 
as  required  by  the  pipe  H. 

In  the  place  of  hydrogen,  Day  states  that  ethylene  or  other  hydrogen- 
carrying  gas  or  vapor  may  be  employed.  By  this  treatment  the  dis- 
agreeable odor  of  hydrocarbon  oil  is  in  great  part  removed  and  the 
burning  qualities  of  the  oil  improved.  When  palladium  black  is  used 
it  is  recommended  that  a  proportion  of  one-half  ounce  to  the  gallon  of 
oil  be  taken. 

Fig.  6  shows  a  modification  of  Day's  process.  A  is  an  oil  still,  in  the 
lower  part  of  which  the  perforated  pipe  H  serves  for  the  admission 
of  hydrogen.  Palladium  black  or  other  porous  absorptive  material 
forms  a  layer  C,  on  a  screen  above  the  hydrogen  inlet.  0  shows  the 
charge  of  oil.  In  operating  this  apparatus  the  layer  of  material  C  is 
first  charged  with  hydrogen  and  then  oil  run  into  the  still.  Distilla- 
tion is  carried  out  while  hydrogen  gas  is  being  forced  through  the 
absorptive  material  and  oil.* 

*  The  removal  of  sulfur  from  petroleum  is  effected  according  to  Schiller  (U.  S. 
Patent  580,652,  April  13,  1897),  by  generating  hydrogen  in  a  nascent  condition  in  the 
oil  during  the  distillation  of  the  latter.  It  is  claimed  that  sulfur  is  thus  eliminated 
as  hydrogen  sulfide.  Zinc  dust  and  an  alkaline  hydrate,  such  as  dry  powdered 
caustic  soda,  are  employed  to  generate  hydrogen.  These  are  added  to  the  oil  under- 
going distillation.  Huston  (U.  S.  Patent  486,406,  Nov.  15,  1892)  proposes  to  re- 
move sulfur  by  heating  the  vapors  of  a  sulfur-containing  petroleum  oil  admixed  with 
steam  to  a  temperature  of  900°  F.  at  which  temperature  it  is  said  that  the  hydro- 
gen of  the  water  vapor  unites  with  the  sulfur,  forming  hydrogen  sulfide.  Hawes 
(U.  S.  Patent  444,833,  Jan.  20,  1891)  avails  of  the  same  reaction  and  brings  a  mixture 
of  vapor  of  hydrocarbon  and  water  into  contact  with  gravel  contained  in  a  chamber 
which  is  heated  to  a  temperature  of  400°  to  600°  F.  Dubbs  (U.  S.  Patent  470,911, 
March  15,  1892)  forces  a  gas  rich  in  hydrogen  through  oil  in  a  still  to  remove  sulfur 
as  hydrogen  sulfide.  Stevens  (U.  S.  Patent  414,601,  Nov.  5,  1889)  claims  steam 
reacts  with  the  sulfur  present  in  petroleum  oils  to  form  sulfurous  acid,  while  the 
hydrogen  thus  liberated  combines  with  the  carbon  of  the  oil,  resulting  in  an  in- 
creased yield  of  light  oil.  See  also  Turner  (U.  S.  Patent  1,046,683,  Dec.  10,  1912)  and 
Noad  (U.  S.  Patent  971,468,  Sept.  27,  1910).  Hall  (U.  S.  Patent  362,672,  Nov.  8, 
1887)  uses  "converting  surfaces"  of  granite.  Wilkinson  (U.  S.  Patent  145,707, 
Dec.  16,  1873)  has  specified  the  distillation  of  petroleum  oils  with  hydrogen. 

The  French  patents  to  Sabatier,  400,141,  and  to  Haller,  Sabatier  and  Senderens, 
376,496,  are  of  interest  in  this  connection. 

In  studying  the  effects  of  catalytic  agents  upon  the  decomposition  of  petroleum 
oils,  100  grams  of  coarsely  powdered  porous  earthenware  upon  which  nickel  had  been 
reduced  in  metallic  form  were  impregnated  with  10  to  12  grams  of  the  oil,  and  heated 


12 


THE  HYDROGENATION  OF  OILS 


The  British  Patent  to  Bedford  and  Williams,  2520,  of  1907,  contains 
probably  the  first  published  description  of  a  method  of  exposing  oil  to 
the  action  of  hydrogen  by  forming  the  oil  in  a  spray  or  films  in  an 
atmosphere  of  hydrogen  and  in  contact  with  a  catalyzer  of  the  nickel 
type.  In  this  manner  the  patentees  state  they  converted  linseed  oil 
into  a  hard  fat  solidifying  at  53°  C.  Oleic  acid  was  converted  into 
stearic  acid  having  a  melting  point  of  69°  C.,  and  paraffin  wax  they 
state  had  its  solidifying  point  raised  3°  C.  by  the  treatment. 

A  peculiar  manner  of  treatment  has  been  shown  by  Schwoerer,* 
which  will  be  made  clear  by  Fig.  7.  The  receptacle  A,  which  is  heated 


FIG.  7. 


FIG.  8. 


by  the  steam  jacket  S,  is  provided  with  what  Schwoerer  calls  a  helical 
pan,  shown  at  B.  The  underside  of  the  pan  carries  a  layer  of  nickelized 
asbestos.  0  is  an  inlet  for  oil  and  hydrogen,  and  D  an  outlet  for  the 
treated  material. 

Schwoerer  states  that  he  first  mixes  fatty  acid  and  hydrogen  by 
atomizing  the  oil  with  a  jet  of  superheated  steam  in  the  presence  of 
hydrogen  and  conducts  this  mixture  through  the  pipe  0,  into  the 
chamber  A.  The  temperature  maintained  in  the  apparatus  is  from 

at  regulated  temperatures  from  180°  to  500°  C.  in  a  current  of  hydrogen.  The  gases 
were  collected  and  analyzed,  while  the  distillates  were  compared  with  those  obtained 
under  parallel  conditions,  but  without  the  presence  of  the  catalytic  agent.  No 
lowering  of  the  vapor  pressure  appeared  to  be  caused  by  the  catalytic  action.  Vari- 
ous proportions  (according  to  the  partial  pressure,  temperature,  etc.)  of  hydrogen, 
methane,  ethane  and  heavy  hydrocarbons  were  produced  under  the  influence  of 
the  catalytic  agent,  while  the  distillates  were  of  quite  different  character  from  those 
yielded  by  the  oil  alone.  Ubbelohde  and  Woronin,  J.  S.  C.  I.,  1911,  1242;  Petro- 
leum 1911  [7],  9. 

*  U.  S.  Patent  902,177,  Oct.  27,  1908. 


METHODS  OF  HYDROGENATION  13 

250°  to  270°  C.  Vapors  of  oleic  acid  come  in  contact  with  the  layer  of 
catalyzer  on  the  underside  of  the  helical  pan  and  are  converted  into 
stearic  acid.  The  product  collects,  more  or  less,  in  the  gutter  of  the 
helical  pan  and  is  removed  at  D. 

The  repeated  caution  given  by  Sabatier  to  bring  in  contact  with  the 
catalyzer  only  the  vapors  of  the  material,  doubtless  led  Schwoerer  to 
devise  this  form  of  apparatus. 

Bedford,  presumably  with  the  same  caution  of  Sabatier  in  mind, 
discloses,  in  U.  S.  Patent  949,954,  of  Feb.  22,  1910,  a  process  which 
also  has  to  do  with  vaporization  of  the  oily  material.  Fig.  8  shows  the 
Bedford  apparatus.  A  still  or  tower  A  carries  two  beds  of  catalyzer 
C  and  C'.  This  is  said  to  be  preferably  nickelized  pumice.  By  means 
of  hydrogen  under  pressure,  oleic  acid  is  sprayed  from  the  pipe  0, 
onto  the  catalyzer  bed  C'.  Hydrogen  is  admitted  through  the  pipe  H. 
A  temperature  of  about  200°  C.  and  a  diminished  pressure  of  about  50 
to  100  mm.  is  maintained  in  the  still  or  tower  A.  The  vapors  of  oleic 
acid  mingled  with  hydrogen  pass  through  the  second  catalyzer  bed  C, 
where  more  or  less  conversion  occurs,  then  pass  to  the  condenser  D,  and 
finally  collect  in  the  receptacle  E.  F  is  a  connection  to  a  vacuum 
pump. 

Neither  this  process  nor  that  of  Schwoerer  is  broadly  applicable 
to  the  treatment  of  glycerides  as  these  cannot  be  vaporized  without 
undue  decomposition.* 

Erdmann  has  taken  out  a  German  Patent  211,669,  of  Jan.  19,  1907, 
involving  passing  an  oil  as  spray  or  mist  into  a  chamber  containing 
nickel  catalyzer  supported  on  pumice  and  the  like.  Fig.  9  probably 
indicates  one  form  suggested  by  Erdmann,  who,  by  the  way,  does  not 
show  any  drawings  in  the  patent.  The  chamber  A  has  a  rotatable 
cylinder  B,  which  is  coated  with  nickel  catalyzer.  In  the  bottom  of 
the  receptacle  is  a  quantity  of  nickelized  pumice.  Oil  enters  at  0  and 
is  atomized  by  hydrogen  entering  at  H.  The  atomized  mixture  im- 
pinges upon  the  rotating  cylinder  B,  then  passes  through  the  bed  C, 
the  oil  being  drawn  off  at  D.  The  excess  of  hydrogen  is  presumably 
vented  in  the  upper  part  of  the  apparatus. 

*  Sabatier  and  Senderens,  Annales  de  Chimie  et  de  Physique  [8],  4,  335  (1905), 
state  that  "Le  m6tal  ne  soit  jamais  mouill6  par  un  afflux  excessif  du  liquide  que 
Ton  traite,  ou  a  la  suite  d'un  abaissement  accidental  de  la  temperature  du  tube." 
They  further  say  that  in  the  preparation  of  cyclohexanol  and  its  homologues  from 
phenol  or  cresol  at  a  temperature  but  slightly  above  the  boiling  points  of  the  latter 
bodies,  sometimes  by  their  condensation,  the  nickel  becomes  moistened  and  imme- 
diately becomes  almost  inactive,  due,  no  doubt,  to  the  surface  becoming  permanently 
changed  in  character  by  contact  with  the  liquid  phenol  or  cresol. 


14 


THE  HYDROGENATION  OF  OILS 


A  second  modification  (Fig.  10)  involves  a  tower  A,  filled  with 
catalyzer  C,  which  may  be  in  the  form  of  nickel  supported  on  coarse 
fragments  of  pumice.  By  the  pipe  0  oil  is  admitted  to  the  chamber 
in  an  atomized  or  finely-divided  state.  Hydrogen  enters  by  the  pipe 


FIG.  9. 


FIG.  10. 


H.  Erdmann  states  that  the  temperature  of  treatment  should  be 
from  170°  to  180°  C.  The  treated  oil  is  drawn  off  at  D  while  the 
excess  of  hydrogen  passes  away  at  B. 

In  a  supplement  patent  221,890,  of  1909,  Erdmann  recommends  the 
steam  distillation  from  the  reaction  chamber  of  the  saturated  product 
under  diminished  pressure. 

Vereinigte  Chemische  Werke  A.  G.*  make  use  of  a  palladium  cata- 
lyzer precipitated  on  an  indifferent  body  as  a  carrier  and  recommend 
as  carriers  finely-divided  metals  which  do  not  have  anti-catalytic 
properties,  also  metal  oxides  and  carbonates.  Under  these  circum- 
stances it  is  stated  that  one  part  of  palladium  is  sufficient  to  convert 
in  a  few  hours  100,000  parts  of  oily  material  to  a  firm  mass.  They 
recommend  the  use  of  a  hydrogen  pressure  of  two  to  three  atmospheres 
and  a  temperature  somewhat  above  the  solidification  point  of  the 
saturated  fat.  They  caution  against  arsenic,  hydrogen  phosphide 

*  German  Patent  236,488,  Aug.  6,  1910;  also  British  Patent  18,642,  1911. 


METHODS  OF  HYDROGENATION 


15 


and  sulfide,  liquid  hydrocarbons  and  carbon  bisulfide,  chloroform, 
acetone  and  free  mineral  acids  as  being  destructive  to  the  activity  of 
the  catalyzer. 

Kayser  *  describes  a  process  of  treating  oil  with  metallic  catalyzer 
consisting  in  mechanically  agitating  the  oil  and  catalyzer  in  the 
presence  of  hydrogen,  preferably  under  pressure.  One  form  of  the 
apparatus  indicated  by  Kayser  for  this  purpose  is  diagrammatically 
represented  by  Fig.  11. 


FIG.  11. 

Here  A  is  a  closed  horizontal  cylindrical  vessel  in  which  is  a  paddle 
wheel  D,  made  up  of  blades  carrying  wire  gauze.  The  paddle  wheel 
is  rotated  by  a  driving  gear  at  B.  In  the  upper  part  of  the  tank  is  an 
inlet  for  charging  oil  and  presumably  also  the  catalyzer,  the  oil  being 
admitted  to  the  tank  in  an  amount  sufficient  to  fill  to  perhaps  one- 
fourth  or  one-fifth  the  entire  capacity.  Hydrogen  is  admitted  at  H 
and  passes,  by  the  three-way  cock  7,  to  the  compression  pump  /,  going 
from  there  to  the  treating  receptacle.  At  the  opposite  end  of  the  tank 
is  an  exhaust  pipe  L,  carrying  a  blow-off  valve  M ,  for  the  purpose  of 
venting  the  unabsorbed  hydrogen.  The  temperature  of  treatment 
is  stated  to  be  about  150°  to  160°  C.  Although  the  claims  call  for  the 
use  of  hydrogen  under  pressure,  no  working  pressures  are  specified. 
Fig.  12  shows  diagrammatically  one  form  of  construction  of  the  screen- 
covered  paddle  wheel  used  by  Kayser. 

In  another  U.  S.  Patent  1,008,474,  of  Nov.  14,  1911,  Kayser  sets 


U.  S.  Patent  1,004,035,  Sept.  26,  1911. 


16 


THE  HYDROGENATION  OF  OILS 


forth  the  use  of  an  inert  pulverulent  material  such  as  kieselguhr  as  a 
carrier  for  the  nickel  catalyzer,  he  apparently  having  determined,  as 
did  Sabatier  and  others,  that  in  some  cases  hydrogenation  is  more  rapid 


FIG.  12. 


\HX 


or  complete  when  a  carrier  for  the  catalyzer  is  used;  and  he  claims  the 
process  of  hydrogenating  oil  involving  agitation  of  a  metal-impreg- 
nated inert  pulverulent  carrier  (kieselguhr)  with  a  fatty  oil  in  the 

presence  of  hydrogen.  It  is  commonly 
understood  that  the  Kayser  process  is 
in  operation  on  a  large  scale  in  this 
country.* 

Two  patents  relating  to  the  spraying 
of  oil  into  a  chamber  containing  com- 
pressed hydrogen  have  attracted  some 
attention  abroad.  One  of  these  is 
British  Patent  7726,  of  1910,  to  Testrup, 
and  the  other  is  to  Wilbuschewitch 
which  finds  its  counterpart  here  in 
U.  S.  Patent  1,024,758,  of  April  30, 
1912.  Fig.  13  shows  the  elements  of 
the  Testrup  process. 

Oil  and  catalyzer  are  pumped  through 

the  pipe  0  into  the  tank  A,  and  hydrogen  is  admitted  by  the  pipe  H 
to  furnish  a  gas  pressure  of,  say,  15  atmospheres.  The  tubes  B  are 

*  The  Kayser  patents  are  assigned  to  the  Proctor  and  Gamble  Co.,  which  concern 
is  a  large  producer  of  hardened  oil.  A  product  termed  "Crisco"  is  used  as  a  sub- 
stitute for  lard. 


v< 


FIG.  13. 


METHODS  OF  HYDROGENATION 


17 


heated  by  steam  and  the  stirrer  C  circulates  the  oil  and  catalyzer  in 
the  tank  A,  until  the  oil  has  become  heated  and  presumably  some- 
what hydrogenated.  The  oil  is  allowed  to  pass  into  the  adjacent 
tank  E,  entering  this  tank  by  the  spray  nozzle  F.  Hydrogen  gas  is 
admitted  to  the  tank  E  from  the  tank  A,  so  as  to  afford  a  pressure 
of,  say,  12  atmospheres  in  the  tank  E.  A  series  of  tanks  may  be 
arranged  with  a  constantly  decreasing  pressure  so  that  the  differential 
pressure  enables  the  spraying  of  the  oil  from  tank  to  tank.  Testrup 
states  that  spraying  the  material  ten  or  fifteen  times  is  sufficient  to 
bring  an  oil  of  an  iodine  number  of  110  down  to  an  iodine  number 
of  50. 


FIG.  14. 


According  to  one  form  employing  the  apparatus  shown  in  Fig.  14,  and  treating 
cottonseed  oil,  the  oil,  mixed  with  a  suitable  contact  substance,  such  as  finely- 
divided  palladium  or  preferably  nickel,  is  placed  in  a  vessel  a  provided  with  a  stir- 
ring device  b  comprising  blades  or  like  elements  fixed  to  a  vertical  and  rotatable  shaft 
c  within  it.  The  amount  of  nickel  may  be  about  2  to  3  per  cent  by  weight.  This 
vessel  is  preferably  jacketed  as  at  d,  and  is  heated  by  the  passage  of  heated  fluid 
through  this  jacket,  say  to  about  160°  C.  From  this  chamber  the  oil  is  pumped  by  a 
pump  e  through  a  conduit /and  enters  a  vessel  g,  which  is  jacketed  and  heated  by  tubes 
h,  being  also  provided  with  a  mixing  device  comprising  a  central  tube  and  propeller 
arrangement  i.  Hydrogen  gas  is  supplied  at  high  pressure  from  a  reservoir  j  through 


18 


THE  HYDROGENATION  OF  OILS 


a  duct  k.  The  vessel  g  has  an  educt  I  for  the  material  under  treatment  at  its  base 
and  an  educt  for  hydrogen  m  provided  with  a  loaded  valve  n.  The  duct  m  opens 
into  a  vessel  o  into  which  the  oil  from  the  vessel  g  is  sprayed  by  a  spray  nozzle  p 
attached  to  the  end  of  the  duct  I  by  the  pressure  of  the  gas  in  the  vessel  g.  The  oil 
and  catalyst  thus  exposed  to  the  action  of  the  gas  fall  into  the  base  of  the  vessel  o 
to  be  forced  by  the  pressure  of  the  gas  therein  through  a  duct  to  a  nozzle  r  in  another 
vessel  s  wherein  the  operation  is  repeated.  Several  such  vessels  are  arranged  in  this 
way  in  cascade,  all  being  jacketed  to  allow  of  maintaining  the  desired  temperature. 
The  last  vessel  I  is  provided  with  any  suitable  educt  u  for  the  gas  and  an  educt  v  for 
the  treated  oil  and  catalyst  which  is  passed  to  a  filter  press  w  in  which  the  oil  is 
separated  from  the  catalyst,  the  former  passing  by  a  duct  z  to  a  reservoir  y  and  the 
catalyst  being  returned  to  the  vessel  a  for  which  purpose  the  chute  z  may  be  utilized. 
Should  the  catalyst  have  become  contaminated  with  nickel  soap  it  may  be  purified  as 
by  washing  with  acid.  A  storage  tank  for  the  material  awaiting  treatment  is  indi- 
cated at  1  with  its  duct  2  leading  to  the  vessel  a.  Gauges  for  noting  the  pressure  3  and 
the  level  gauges  4  are  also  employed.  The  temperature  at  which  the  reaction  is  con- 
ducted is  about  160°  to  170°  C.,  and  the  pressure  of  the  hydrogen  in  g  maybe  about 
15  atmospheres,  in  o  say  12  atmospheres,  the  difference  in  pressure  producing  the 
spray.  The  pressure  may  similarly  fall  by  3  atmospheres  for  each  vessel.  It  may 
be  necessary  to  pass  the  substance  again  through  the  ap- 
paratus or  to  provide  several  systems  of  heaters  and 
spraying  devices  in  series  in  order  to  obtain  the  desired 
result  but  by  this  process  the  desired  number  of  repe- 
titions can  be  carried  out  rapidly.* 

Even  such  a  number  of  treatments  are  stated  to  re- 
quire only  about  30  minutes  or  less  and  the  number  of 
treatments  would  depend  largely  on  the  activity  of  the 
catalyst  employed. 

The  Wilbuschewitch  Patent  itself  details  a 
rather  complicated  system,  and  Fig.  15  shows 
only  what  appears  to  be  the  essential  features 
of  the  treating  apparatus.  Several  tanks  or 
autoclaves  are  connected  as  shown  at  A  and 
A',  oil  entering  the  top  of  the  tank  A  by  the 
pipe  0,  to  form  a  spray  which  in  descending 
meets  an  upward  current  of  hydrogen  entering  by  the  pipe  H.  The 
oil  is  drawn  off  through  the  pipe  0',  and  sprayed  into  the  tank  A'. 
This  time  it  meets  a  current  of  hydrogen  represented  by  the  excess  of 
hydrogen  coming  from  the  tank  A.  The  treated  oil  is  drawn  off  and 
may  be  centrifuged  to  remove  the  catalyzer.  A  pressure  of  nine 
atmospheres  is  recommended  and  the  pressures  may  be  varied  in  the 
different  tanks. 

*  Swedish  Patent  992,  May  27,  1911  (Techno  Chemical  Laboratories,  Ltd.),  on 
the  hydrogenation  of  organic  substances  involving  a  process  which  essentially  con- 
sists in  mixing  catalyzer  with  the  substance  to  be  treated  and  in  subjecting  the 
mixture  in  an  atomized  or  finely-divided  condition  to  the  action  of  hydrogen,  leads 


FIG.  15. 


METHODS  OF  HYDROGENATION 


19 


Of  the  Wilbuschewitch  process  Goldschmidt  *  states  that  the  high 
hydrogen  pressures  employed  enable  the  reaction  to  take  place  quickly 
at  temperatures  between  100°  and  160°  C.,  so  that  the  fat  is  not  likely 
to  be  injured  by  the  temperature  to  which  it  is  subjected.  It  should 
be  stated  that  several  years  previous  to  the  date  of  the  Wilbusche- 
witch patent,  Ipatiew  had  noted  and  carefully  studied  the  action  of 
increased  pressure. 

Bedford  and  Williams  have  brought  out  an  interesting  process 
represented  by  U.  S.  Patent  1,026,339,  of  May  14,  1912.  Fig.  16 
shows  the  apparatus  indicated  by  Bedford  and  Williams  for  carrying 
out  the  process.  Oil  is  placed  in  the  receptacle  A,  which  is  heated  by 


FIG.  16. 


FIG.  17. 


a  steam  coil  S.  Metallic  oxide  catalyzer  is  added,  about  1  per  cent 
being  recommended,  and  hydrogen  and  oxygen  or  air  is  introduced 
by  the  pipe  H.  As  a  catalyzer,  nickel  oxide  f  is  recommended  and 
instead  of  the  customary  hydrogenating  temperatures  of  150°  to 
170°  C.,  a  temperature  of  about  250°  C.  is  employed.  While  hydro- 
gen alone  may  be  used  for  the  purpose,  the  inventors  recommend  and 
claim  treatment  of  the  oil  with  a  mixture  of  hydrogen  and  oxygen  to 
form  hydroxy  fatty  acids  or  their  glycerides. 

A  process  for  the  conversion* of  fatty  acids  or  their  glycerides  into 
saturated  bodies  in  which  a  finely-divided  metal  oxide  serves  as  a 
catalyzer  is  described  by  Bedford,  Williams  and  Erdmann,  I  and  the 
reaction  is  carried  out  under  pressures  ranging  from  atmospheric 
pressure  up  to  but  not  exceeding  20  atmospheres.  Nickel  oxide  is 
especially  recommended  as  the  catalytic  material. 

the  editor  of  Chemiker  Zeitung  (Chem.  Zeit.  Rep.  (1913),  320)  to  make  the  comment 
that  it  is  somewhat  questionable  according  to  other  investigations  which  have  been 
made  in  this  direction,  whether  this  process  is  practical  for  the  manufacture  of 
edible  fats  and  the  like. 

*  Chem.  Ztg.,  1912,  945. 

t  Previously  used  by  Ipatiew. 

I  Siefen.  Ztg.,  1913,  1413. 


20  THE  HYDROGENATION  OF  OILS 

Shukoff  *  claims  the  process  of  hydrogenating  oils  by  means  of  nickel 
derived  from  the  decomposition  of  nickel  carbonyl.  The  carbonyl 
may  be  obtained  from  reduced  metallic  nickel  by  passing  carbon 
monoxide  over  it  at  a  low  temperature.  Nickel  carbonyl  is  soluble  in 
oil  and  is  very  readily  taken  up  by  gases.  On  heating  to  a  tempera- 
ture of  200  degrees  or  so,  the  carbonyl  is  decomposed,  setting  free,  in 
a  nascent  state,  metallic  nickel  which  acts  as  a  catalyzer.  Shukoff 
makes  use  of  this  reaction  of  nickel  carbonyl  by  the  method  indicated 
by  Fig.  17.  Carbon  monoxide  is  passed  by  the  pipe  G  into  the  tube 
B,  containing  finely-divided  nickel  and  the  nickel  carbonyl  formed  is 
conducted  to  the  oil  0,  which  is  heated  to  about  180  degrees.  After 
sufficient  nickel  catalyzer  has  formed  in  the  oil,  the  carbon  monoxide 
stream  is  cut  off,  the  temperature  raised  to  220°  or  240°  C.  and  hydro- 
gen gas  introduced  by  the  pipe  H  to  bring  about  hydrogenation. 

Schukoff  states  if  nickel  carbonyl  in  a  gaseous  condition  or  a  nickel- 
carbonyl-containing  gas  mixture  is  conducted  into  the  material  to  be 
reduced,  which  may  be  either  in  a  molten  condition  or  in  solution  in  a 
suitable  solvent,  it  is  found,  when  the  temperature  advances  beyond 
the  temperature  of  dissociation  of  nickel  carbonyl,  that  metallic  nickel 
in  an  extremely  finely-divided  state  is  separated  and  that  the  division 
obtained  in  this  way  is  so  fine  as  to  cause  the  reaction  mixture  to 
appear  black  in  color,  and  the  separated  nickel  settles  only  after  very 
long  standing.  As  an  example :  Into  8  kilos  of  cottonseed  oil  warmed 
to  180°  C.  a  slow  stream  of  400  liters  of  carbon  monoxide  is  passed, 
which  carbon  monoxide  has  previously  passed  over  a  long  layer  of 
metallic  nickel  warmed  to  about  60°  C.;  finely-divided  active  nickel 
separates  in  the  oil;  the  stream  of  carbon  monoxide  is  then  inter- 
rupted, the  temperature  raised  to  230°  to  240°  C.,  and  hydrogen  as 
a  slow  stream  is  run  into  the  mixture  during  a  period  of  five  to  six 
hours  in  an  amount  of  3000  liters.  The  reaction  mixture  on  cooling 
is  completely  hard;  by  filtration  the  nickel  can  be  removed  and  the 
product  eventually  converted  into  stearic  acid. 

Day  has  taken  out  U.  S.  Patent  1,004,632,  of  Oct.  3,  1911,  supple- 
menting his  earlier  patent  on  the  treatment  of  hydrocarbon  oils  with 
hydrogen.  In  the  present  instance  tubes  packed  with  catalyzer  are 
placed  in  an  oil  still  in  such  a  manner  that  vapors  from  the  oil  may  pass 
through  the  catalyzer  tube  in  conjunction  with  hydrogen  while  being 
superheated  by  exterior  contact  of  the  tubes  with  boiling  oil. 

An  English  Patent,  23,997,  of  1909,  to  Phillips  and  Bulteel  claims 

*  German  Patent  241,823,  Jan.  18,  1910.  See  also  H.  Kamps,  Belgian  Patent 
246,975;  Seifen.  Ztg.,  1912,  1339.  U.  S.  Patents,  738,303,  777,848  and  943,627  are 
of  incidental  interest. 


METHODS  OF  HYDROGENATION 


21 


to  convert  mineral  oils  into  oils  of  lower  specific  gravity  by  heating 
with  hydrogen  in  the  presence  of  nickel  or  other  catalytic  agents. 
They  state  that  the  mixture  of  oil,  gas  and  catalyst  may  be  blown  into 
a  heated  cylinder  and  the  jet  given  a  gyratory  motion  either  by  means 
of  a  nozzle  revolving  about  its  axis  or  by  injecting  the  mixture  tan- 
gentially  to  the  periphery.  In  the  latter  case  they  state  that  the 
cylinder  may  have  an  axial  core.* 

The  firm  of  H.  Schlinck  &  Co.,  of  Hamburg,  Germany, |  hydrogenate 
oil  by  passage  through  a  centrifuge,  the  drum  of  which  carries  a  porous 
lining  supporting  palladium  catalyzer  which  offers  a  frictional  resist- 
ance to  the  passage  of  the  oil.  Fig.  18  shows  a  centrifugal  drum  a, 
which  is  closed  at  the  top  and  can  be  heated.  Oil  and  hydrogen  are 
introduced  through  the  pipe  6.  Openings  are  provided  in  the  walls 
of  the  drum  in  which  is  placed  rough  or  porous  material  covered  with 
precipitated  palladium.  Several  drums  may  be  arranged  in  series 


FIG.  18. 


FIG.  19. 


*  In  the  treatment  of  hydrocarbons  with  superheated  steam  Hausmann  and 
Pilat  (German  Patent  227,178,  1909)  recommend  as  catalyzers  the  oxides  of  iron, 
lead,  cerium  and  manganese,  also  iron  sulfate  and  calcium  manganite.  Richter 
(German  Patent  240,760,  1910)  makes  use  of  active  carbon  as  a  carrier  for  oxygen 
in  the  treatment  of  petroleum  and  other  oils.  Leffer  (British  Patent  2328,  1912) 
distils  petroleum  oil  under  pressure  while  circulating  an  inert  gas  through  the  body 
of  oil  in  the  still.  Leffer  mentions  hydrogen  among  the  inert  gases  suitable  for 
the  purpose.  Lamplough  (British  Patent  19,702,  1912)  proposes  to  effect  reaction 
between  petroleum  oil  and  water  by  passing  a  mixture  of  the  vapors  of  these  bodies 
over  rods  of  metallic  nickel  while  subjecting  .the  vapors  to  a  pressure  and  to  a  tem- 
perature approaching  a  dull  red  heat.  From  20  to  60  parts  of  water  are  used  to  100 
parts  of  oil.  Dibdin  and  Woltereck  (British  Patent  19,152,  1901)  bring  a  mixture 
of  superheated  steam  and  petroleum  oil  into  contact  with  iron,  copper  and  other 
metals  maintained  at  a  bright  orange  heat  to  effect  the  simultaneous  decomposition 
of  the  steam  and  hydrocarbon.  They  also  mention  (British  Patent  26,666,  1905) 
the  use  of  " protoperoxide "  of  iron. 

t  British  Patent  8147,  1911.  The  corresponding  patent  in  the  United  States  is 
1,082,707,  Dec.  30,  1913. 


22 


THE  HYDROGENATION  OF  OILS 


through  which  the  oil  may  be  caused  to  progress  until  sufficiently 
hydrogenated. 

Ellis  *  uses  a  stationary  catalyzer,  filling  tubes  with  the  material  in 
granular  form  and  allowing  oil  to  flow  through  the  tubes  while  passing 
hydrogen  in  an  opposite  direction.  Fig.  19  shows  a  three-section 
apparatus  with  the  catalyzer  tubes  T,  T1  and  T2,  heated  by  the  jackets 
SS.  Oil  from  tank  0  flows  through  the  apparatus  while  hydrogen, 
admitted  by  the  pipe  H,  passes  through  in  an  opposite  direction. 
The  arrangement  permits  of  differential  heating  so  that,  for  example, 
the  oil  may  be  heated  to  a  temperature  corresponding  to  its  particular 
degree  of  hydrogenation  at  any  given  point,  enabling  a  hydrogenated 
product  free  from  "  burnt  "  odor  to  be  obtained.  Fig.  20  shows  a  ver- 
tical form  of  apparatus,  the  catalyzer  being  shown  at  C  in  the  tube  A. 


»-  ••$ 
*  k- 


I ,  ffrft 


(D 


FIG.  20. 


FIG.  21. 


Oil  is  introduced  by  the  pipe  0,  and  passes  into  the  tube  or  cylinder  A. 
The  pump  P  causes  oil  to  circulate  from  the  top' to  the  bottom  of 
the  apparatus  through  the  pipe  B.  Hydrogen  gas  admitted  at  H  is 
pumped  into  the  bottom  of  the  cylinder  A,  and  the  excess  is  withdrawn 
at  the  top  by  the  pipe  D,  passing  through  the  drier  E,  and  back  into 
the  treating  cylinder.  Oil  may  be  continuously  fed  through  the  pipe 
0  in  the  upper  part  and  the  treated  product  withdrawn  at  the  same 
rate  at  the  lower  part  of  the  apparatus. 

In  another  form  f  of  the  apparatus,  the  catalyzer  is  placed  in  trays 
or  baskets  as  shown  by  Fig.  21  at  C.  The  oil  travels  in  a  cyclic  path 
downward  through  several  layers  of  catalyzer,  and  hydrogen  gas  passes 
in  an  opposite  direction.  Separation  of  the  catalyzer  in  layers  in  this 
manner  enables  the  hydrogen  to  pass  more  uniformly  through  the 

*  U.  S.  Patent  1,026,156,  May  14,  1912.  See  also  U.  S.  Patent  1,052,469,  Feb. 
11,  1913. 

t  U.  S.  Patent  1,040,531,  Oct.  8,  1912. 


METHODS  OF  HYDROGENATION 


23 


catalyzer  bed.  If  the  catalyzer  forms  a  bed  of  considerable  depth  and 
width,  the  gas  in  taking  the  path  of  least  resistance  is  liable  not  to 
come  in  contact  with  some  parts  of  the  bed. 

The  activity  of  a  properly  made  catalyzer  is  oftentimes  surprising. 
In  the  case  of  a  stationary  catalyzer  the  author  has  noted  instances  of 
hydrogenation  where  oil  is  converted  into  a  hardened  fat  by  scarcely 
more  than  momentary  contact  with  the  catalyzer. 

Fig.  22  shows  a  photograph  of  a  small  laboratory  apparatus  for  test- 
ing catalyzers,  consisting  of  an  inclined  tube  containing  the  catalyzer 
and  carried  in  a  heating  jacket.  Oil  is  admitted  at  the  right  and 
hydrogen  at  the  left-hand  end.  Fig.  23  shows  the  catalyzer  tube  at 
the  right  from  which  extends  a  horizontal  tube  supplying  hydrogen 
to  the  catalyzer  tube. 


FIG.  22. 


When  using  a  new  type  of  catalyzer  the  author  started  to  pass  oil 
through  the  catalyzer  tube  and  found  hydrogen  to  be  absorbed  so 
vigorously  by  the  oil  that  instead  of  passing  off  through  an  oil  seal  at 
the  lower  end  of  the  inclined  catalyzer  tube,  the  oil,  curiously  enough, 
was  impelled  against  the  strong  current  of  hydrogen  passing  through 
the  horizontal  tube,  rushing  through  it  to  the  point  indicated  by  the 
hand  of  the  operator  (Fig.  23)  and  there  solidifying,  actually  being 
well  hydrogenated  from  its  brief  passage  through  the  apparatus.  A 


24 


THE  HYDROGENATION  OF  OILS 


peculiar  feature  was  the  advance  of  the  oil  from  the  tube  containing 
catalyzer  far  into  the  tube  through  which  only  the  hydrogen  was 
entering  the  apparatus.  The  travel  of  the  oil  along  the  hydrogen- 
supplying  pipe  in  opposition  to  a  rapid  current  of  hydrogen  indicates 
the  possibility  of  hydrogenating  in  a  very  short  time,  provided  a  cata- 
lyzer of  a  high  degree  of  activity  is  secured. 


FIG.  23. 


On  the  other  hand,  some  catalyzers  of  the  nickel  and  cobalt  type 
when  first  brought  into  contact  with  oil  and  hydrogen  show  for  a  time 
a  certain  degree  of  sluggishness,  but  after  a  period,  their  activity 
rather  suddenly  augments  and  thenceforth  remains  apparent  for  a 
long  period.  This  sluggishness  should  not  be  confounded  with  the 
seeming  initial  inactivity  in  the  hydrogenation  of  oils  containing  con- 
siderable linolein  or  other  highly  unsaturated  bodies.  In  such  cases 
the  rate  of  "  hardening  "  (increase  in  melting  point)  is  slow  at  first 
and  later  progresses  more  rapidly.  Hydrogenation,  in  some  cases  at 
least,  apparently  proceeds  selectively  with  initial  formation  of  olein 
from  linolein.  Later  the  olein  is  transformed  into  stearin  with  the 
observed  more  rapid  increase  of  titer.* 

*  Mailhe  (Rev.  gen.  des  Sciences,  1913,  653)  makes  note  that  he  has  seen  cotton- 
seed oil  hardened  to  a  high  titer  by  twenty  minutes  exposure  to  hydrogen  and  cata-  | 
lytic  material. 


METHODS  OF  HYDROGENATION 


25 


Marcusson  and  Meyerheim  *  have  reached  the  conclusion  that  fish 
oil  (tran)  does  not  hydrogenate  selectively  or  by  stages,  that  is  to  say, 
the  more  highly  unsaturated  components  do  not  largely  take  up  hydro- 
gen before  olein  becomes  converted  into  stearin.  A  certain  percentage 
of  the  highly  unsaturated  fatty  acids  remain  even  after  a  large  propor- 
tion of  the  oleic  acid  has  been  transformed  into  stearic  acid.  The  inner 
iodine  number  (iodine  number  of  the  liquid  fatty  acids)  of  a  sample  of 
hardened  tran  was  found  to  be  107,  which  result  led  to  the  foregoing 
conclusion. 

Ellis  f  effects  a  constant  circulation  and  contact  of  the  hydrogen 
gas  in  accordance  with  the  method  shown  by  Fig.  24.  The  tank  A 
contains  a  body  oil  0,  the  space  above  the  oil  being  filled  with  hydro- 
gen under  any  suitable  pressure.  The  tank  is  heated  by  the  jacket  S. 
A  pump  P  withdraws  the  hydrogen  from  the  upper  part  of  the  tank 
and  impels  it  through  the  pipe  D  into  the  lower  part  of  the  tank.  The 
catalyzer  is  added  to  the  oil  when  the  proper  temperature  is  reached 
and  the  constant  bubbling  of  a  stream  of  hydrogen  through  the  oil 
causes  intimate  contact  between  the  reacting  elements.  After  the 


FIG.  24. 


FIG.  25. 


operation  is  completed,  the  porous  plate,  fastened  to  a  movable  stem 
in  the  upper  part  of  the  tank,  may  be  depressed  to  fit  into  the  bottom 
of  the  conical  base  so  that  when  the  oil  is  withdrawn  a  good  portion  of 
the  catalyzer  remains  without  exposure  to  the  air  and  may  be  used 
with  perhaps  a  small  addition  of  fresh  catalyzer  for  the  treatment 
of  a  succeeding  charge  of  oil. 

In  U.  S.  Patent  1,043,912,  Ellis  hydrogenates  oil  (Fig.  25)  in  the 
autoclave  A.  The  pump  P  circulates  hydrogen  gas  through  the  oil. 
The  treated  product  is  run  into  the  deodorizer  D,  where  it  is  treated 

*  Zeitsch.  f.  angew.  Chem.  1914,  No.  28,  201. 
t  U.  S.  Patent  1,059,720,  April  22,  1913. 


26  THE  HYDROGENATION  OF  OILS 

with  superheated  steam  under  diminished  atmospheric  pressure  until 
the  oil  is  freed  from  noxious  gases  or  vapors.  While  the  deodorization 
of  ordinary  cottonseed  oil,  for  example,  requires  a  temperature  from 
200°  to  300°  C.  and  a  vacuum  of  down  to  one  or  two  inches  mercury, 
the  deodorization  of  the  hydrogenated  cottonseed  oil  does  not  neces- 
sarily require  as  high  a  temperature  and  the  vacuum  "  pulled  "  may 
be  considerably  less. 

Contrary  to  the  opinion  entertained  by  many  it  does  not  appear 
needful  to  violently  agitate  the  catalyzer  primarily  for  the  purpose  of 
contacting  it  with  hydrogen.  Once  the  catalyzer  is  wetted  with  the 
oil  there  can  no  longer  be  any  actual  contact  with  the  gas.  Hydrogen 
reaches  the  catalyzer  seemingly  only  through  solution  in  the  oil.  The 
forces  of  adhesion  effectually  seal  the  catalyzer  surface  from  the  gas, 
and  no  measure  of  agitation  by  ordinary  mixing  apparatus  will  dis- 
lodge the  film  of  oil.  Of  course,  agitation  secures  the  rapid  replace- 
ment of  more  saturated  by  less  saturated  portions  of  the  oil,  but  this 
replacement,  under  certain  conditions,  may  proceed  rapidly,  simply 
by  diffusion. 

The  direct  pumping  of  hot  hydrogen  gas,  especially  if  the  latter  is 
under  considerable  pressure,  offers  some  difficulties,  and  the  apparatus 
shown  in  Fig.  26  is  designed  to  effect  a  circulation  of  the  gas  by  in- 
ductive effect.*  The  tank  1  carries  an  inductor  2  through  which  is 
forced  oil  propelled  by  the  pump  3.  The  passage  of  the  oil  through 
the  inductor  causes  hydrogen,  which  is  supplied  to  the  upper  part 
of  the  tank,  to  be  drawn  into  the  central  vertical  pipe  and  carried  with 
the  oil  to  the  bottom  of  the  tank  when  the  gas  bubbles  through  the 
main  body  of  oil.  Thus  the  oil  which  is  being  treated  is  made  use  of 
to  circulate  the  gas. 

Another  type  of  apparatus  f  involves  circulating  hydrogen  gas  by 
means  of  an  oil  sealed  pump  which  may  be  so  arranged  as  to  permit 
the  return  of  any  hydrogen  escaping  through  the  stuffing  boxes.  Fig. 

27  shows  this  apparatus.     1  is  an  oil  treating  tank  with  gas  outlet  2, 
communicating  with  a  drier  or  purifier  3.     From  the  lower  part  of 
the  latter  a  pipe  leads  to  the  pump  4  which  is  enclosed  by  the  housing 
5,  the  space  between  pump  and  housing  being  filled  with  oil.     The 
pump  discharges  into  the  lower  part  of  the  tank  through  the  gas  dis- 
tributor 6.     A  connection  7  from  the  upper  part  of  the  housing  to  the 
tank  provides  a  vent  for  gas  escaping  from  the  pump. 

In  hydrogenating  oleic  acid  in  a  vaporized  state  Shawt  obtained 

*  U.  S.  Patent  to  Ellis,  1,059,720,  April  22,  1913. 
f  U.  S.  Patent  to  Ellis,  1,071,221,  Aug.  26,  1913. 
J  Seifen.  Ztg.,  1912,  713. 


METHODS  OF  HYDROGENATION 


27 


some  rather  curious  results.  As  a  hydrogenating  apparatus  Shaw 
used  a  glass  tower,  holding  catalyzer,  the  latter  being  prepared  by  put- 
ting fragments  of  pumice  into  a  50  per  cent  solution  of  nickel  nitrate. 
The  pumice  was  heated  to  a  red  heat  in  order  to  convert  the  nitrate 

to  the  oxide  and  the  process  re- 
peated in  order  to  get  a  good 
coating.  The  material  was  then 
placed  in  the  glass  tower  and  re- 
duced by  hydrogen  at  about  300° 
C.,  reduction  taking  place  in  2  to 
3  hours.  The  tower  was  heated 
in  an  oil  bath. 

Oleic  acid  was  supplied  from 
a  distilling  flask  which  was  con- 


FIG.  26. 


FIG.  27. 


nected  with  the  tower  by  gas-tight  piping.  In  the  flask  was  inserted  a 
tube  through  which  hydrogen  could  be  introduced.  The  hydrogen  was 
generated  in  a  Kipp  apparatus,  passed  through  wash  bottles  contain- 
ing nitric  acid  and  sulfuric  acid,  and  finally  through  a  "  U  "  tube 
containing  fragments  of  caustic  potash.  From  the  tower  a  delivery 
tube  extended  to  a  receiver  which  was  connected  with  a  manometer 
and  an  air  pump.  The  temperature  of  the  oleic  acid  was  maintained 
a  few  degrees  above  the  boiling  point  of  the  acid,  or  about  300°  C.  In 
this  way  the  catalyzer  was  never  wetted  with  the  liquid  acid,  but  came 
in  contact  only  with  the  gaseous  acid  which  distilled  over  from  the 
flask.  The  reaction  product  was  condensed  in  the  receiver. 


28  THE  HYDROGENATION  OF  OILS 

The  degree  of  reduction  was  determined  through  the  iodine  num- 
ber with  the  following  results:  the  iodine  number  of  oleic  acid 
employed  was  79.  When  distilled  under  a  pressure  of  100  mm.,  the 
resulting  product  had  an  iodine  number  of  75,  which  corresponds  to 
a  reduction  of  5  per  cent.  This  partially  reduced  product  under  a 
pressure  of  100  mm.  was  distilled  through  the  catalyzer,  and  the  prod- 
uct obtained  had  an  iodine  number  of  74.8,  practically  identical  with 
the  previous  value.  In  reviewing  this  unfavorable  result  it  was  con- 
cluded that  the  catalyzer  was  poisoned  and  its  activity  lost.  To  test 
this  out  a  fresh  portion  of  oleic  acid  was  distilled  through  the  catalyzer. 
Again  a  reduction  of  5  per  cent  occurred,  which  indicated  that  the 
catalyzer  was  not  poisoned. 

Distillation  at  150  mm.  was  then  tried,  giving  a  reaction  product 
having  an  iodine  number  of  68  to  70.  When  this  product  was  distilled 
again  at  150  mm.,  the  same  iodine  number  was  obtained.  A  pressure 
of  200  mm.  was  then  employed  and  the  reduction  was  20  per  cent,  while 
a  second  distillation  at  200  mm.  did  not  increase  the  amount  reduced. 

These  results  suggested  the  possibility  of  an  equilibrium  between 
stearic  acid,  oleic  acid  and  hydrogen,  and  that  the  reduction  degree 
which  Shaw  found  varied  from  pressure  to  pressure  was  constant  for 
any  one  pressure.  If  this  conclusion  were  correct,  then  the  equi- 
librium should  be  reached  from  the  opposite  end,  namely  through 
distilling  stearic  acid  in  the  presence  of  hydrogen.  In  order  to  see 
whether  this  were  possible  stearic  acid  was  treated  in  exactly  the  same 
way  as  the  oleic  acid  by  distilling  through  freshly  prepared  catalyzer. 
As  a  result  of  the  test  it  appeared  that  stearic  acid  experienced  no 
change  in  iodine  number  which  apparently  excluded  the  idea  that 
conditions  of  equilibrium  were  involved. 

Shaw's  observations  that  by  repeated  distillation  of  oleic  acid  no 
further  reduction  occurs  was  not  to  be  explained  on  the  ground  of 
fractional  distillation  of  the  partially  reduced  product,  for  the  entire 
contents  of  the  flask  were  distilled  through  the  catalyzer,  and  further- 
more the  boiling  point  of  stearic  acid  differs  very  little  from  oleic  acid, 
so  Shaw  is  at  a  loss  to  explain  the  cause  of  this  peculiar  behavior  after 
finding  it  not  due  either  to  the  existence  of  equilibrium  or  fractional 
distillation. 

An  investigation  was  made  to  determine  what  influence  length  of 
time  had  on  the  progress  of  reduction.  The  same  apparatus  was  used. 
Oleic  acid  was  distilled  under  diminished  pressure  and  the  tempera- 
ture of  the  oil  bath  maintained  at  275  degrees,  while  small  quantities 
of  the  acid  were  distilled  over  in  definite  time  intervals  and  the  iodine 
number  determined. 


METHODS  OF  HYDROGENATION  29 

The  following  is  the  result : 

2    hours  Iodine  No.  67  M.  P.  23° 

:U  hours  Iodine  No.  62  M.  P.  33° 

5    hours  Iodine  No.  60  M.  P.  37° 

9    hours  Iodine  No.  45  M.  P.  50° 

Shaw  also  determined  the  effect  of  pressure  considerably  above 
atmospheric  and  found: 

With  pressure  of  5  atmos.;  temp.  250°  C.;  Iodine  No.  77 
With  pressure  of  25  atmos.;  temp.  250°  C.;  Iodine  No.  64 
With  pressure  of  50  atmos.;  temp.  250°  C.;  Iodine  No.  52 

by  which  he  concludes  that  the  reduction  progresses  in  proportion  to 
the  increase  in  pressure.* 

»In  the  decomposition  of  fats,  oils  and  waxes  into  fatty  acids  and 
alcohols  by  aromatic  sulfonated  fatty  acids,  the  fats  or  fatty  acids 
used  in  preparing  the  latter,  according  to  Connstein  and  von  Schon- 
than,  are  reduced  before  sulfonation,  either  by  catalytic  processes  or 
by  electrolysis. f  For  example,  castor  oil  is  hardened  by  treatment 
with  hydrogen,  using  palladium  catalyzer;  equal  parts  of  the  hardened 
product  and  naphthalene  are  mixed  and  to  the  mixture  twice  its  weight 
of  sulfuric  acid  of  66°  Baume  is  added,  avoiding  an  increase  of  tem- 
perature above  20°  C* 

The  reaction  mixture  is  stirred  until  homogeneous  and  is  then  poured 
into  somewhat  more  than  its  own  weight  of  water.  The  oily  layer 
which  separates  is  filtered  and  is  then  ready  for  use.  An  illustrative 
example  of  the  process  by  the  patentees  calls  for  treatment  of  1000 
parts  of  palm  kernel  oil,  300  parts  of  water  and  2  parts  of  the  fat 
cleavage  compound  for  6  to  8  hours  with  dry  steam.  After  separation 
of  the  two  layers  the  lower  layer  or  glycerine  water  is  concentrated 
in  the  customary  manner  while  the  upper  layer  consists  of  fatty  acids. 

According  to  Steffan  J  this  fatty  cleavage  reagent  has  been  placed 
on  the  market  under  the  name  of  *  *  Pf  eilring."  §  Steffan  comments 
on  the  discoloring  action  of  the  Twitchell  process  on  some  fats  and  oils 
among  which  he  mentions  certain  grades  of  tallow,  soya  bean  oil  and 
fish  oil,  the  coloration  of  whose  fatty  acids  when  produced  by  the 

*  Sabatier  notes  in  his  book  on  Catalysis,  Paris,  1913,  78,  that  the  vapors  of  oleic 
acid  entrained  by  a  strong  current  of  hydrogen  and  passed  over  nickel  heated  to 
280°  to  300°  C.  are  rapidly  transformed  into  stearic  acid,  and  the  same  thing  occurs 
with  the  isomer  elaidic  acid.  (See  Ann.  Chim.  Phys.  (8),  16,  73,  1909.) 

t  British  Patent  749,  Jan.  10,  1912,  Vereinigte  Chem.  Akt.  Ges. 

j  Seifen.  Ztg.,  40,  550. 

§  "Pf eilring"  cleavage  composition  from  the  patent  standpoint  is  critically 
discussed  by  Esch  (Chem.  Rev.  u.  d.  Fett  u.  Harz  Ind.  (1913),  295). 


30  THE  HYDROGENATION  OF  OILS 

Twitchell  process  being  so  dark  that  when  made  into  soaps  the  color 
of  the  product  leaves  much  to  be  desired. 

Fat  cleavage  reagent  prepared  with  the  hardened  oil  is  claimed  to 
produce  a  much  lighter  fatty  acid.  The  rate  of  saponification  with 
the  hardened  oil  product  Pfeilring  is  approximately  that  of  the 
Twitchell  reagent.  Using  equal  parts  of  the  two  reagents  under  like 
conditions  the  following  results  were  obtained: 

5  hours,          23J  hours,         34  hours, 
per  cent  per  cent  per  cent 

Twitchell  reagent 37.23  83 .31  88 .94 

Pfeilring  reagent 36 . 92  80 . 18  88 . 69 

These  results  indicate  for  Pfeilring  a  rate  of  cleavage  slightly  less 
than  that  of  the  Twitchell  reagent,  but  it  is  brought  forward  by  the 
supporters  of  Pfeilring  that,  the  latter  reagent  being  in  itself  very  light 
colored,  while  the  Twitchell  reagent  has  a  blackish  cast,  the  propor- 
tion of  the  latter  which  may  be  used  is  limited  by  the  required  color  of 
the  resulting  fatty  acids,  but  that  Pfeilring  may  be  used  in  larger  pro- 
portion without  the  danger  of  discoloration  and  hence  the  rate  of 
cleavage  may  be  increased  by  using  a  larger  quantity  of  the  reagent 
while  the  reaction  may  be  carried  more  nearly  to  completion,  that  is 
to  95  per  cent  and  over,  without  the  discoloration  sometimes  observed 
in  the  Twitchell  process. 

In  response  to  a  critical  discussion  of  the  properties  of  soaps  made 
with  hardened  oils  *  Sudf eldt  Brothers  state  f  that  for  several  years 
they  have  been  splitting  large  quantities  of  hardened  whale  oil  by  the 
Twitchell  process  and  converting  the  fatty  acids  into  soap  and  have 
found  these  fatty  acids  to  be  of  good  color  and  the  soaps  prepared 
from  them  to  be  in  no  wise  lacking  in  color.  The  sharp  odor  noticed 
in  the  neutral  fat  is  not  lost  by  the  splitting  operation  and  also  appears 
in  the  finished  soap.J 

Reference  has  been  made  to  the  work  of  DeHemptinne  on  the  effect 
of  electrical  discharge  in  causing  the  addition  of  hydrogen  to  unsatu- 
rated  oils.  Later  work  by  this  investigator  §  furnishes  additional 
data  on  this  interesting  reaction.  The  formation  of  stearin  by  the 
action  of  an  electric  discharge  on  commercial  olein  in  an  atmosphere 
of  hydrogen  was  studied  on  both  a  small  and  large  scale.  The  appara- 
tus employed  on  a  large  scale  consists  of  a  rotatable  horizontal  axle 

*  Seifen.  Ztg.  No.  25,  1912. 
t  Seifen.  Ztg.  (1912),  720. 

t  Sudf  eldt  &  Co.  contend  in  favor  of  the  Twitchell  reagent;  Seifen.  Ztg.  (1913), 
613.     See  also  Seifen.  Ztg.  (1914),  311,  338  and  392. 
§  Bull.  Soc.  Chim.  belg.,  26,  55. 


METHODS  OF  HYDROGENATION  31 

bearing  a  large  number  of  thin,  parallel,  vertical  iron  plates  separated 
by  glass  plates,  the  former  being  connected  together  alternately  on 
opposite  sides.  The  whole  is  mounted  in  an  air-tight  iron  drum  which 
is  partially  filled  with  olein  and  into  which  hydrogen  is  introduced; 
the  odd  numbers  of  the  iron  plates  are  connected  with  one  pole  of  a 
high-potential  alternator  and  the  even  numbers  with  the  other  pole. 
When  the  axle  is  rotated,  the  electric  discharge  passes  through  a  thin 
layer  of  olein  which  constantly  wets  the  plates.  The  glass  dielectric 
may  be  arranged  so  as  to  contact  with  one  or  both  faces  of  the  iron 
plates  (the  free  space  in  the  latter  case  being  between  the  dielectrics) 
or  the  dielectrics  may  be  separated  from  both  faces  of  the  iron  plates. 
The  capacity  of  the  largest  apparatus  constructed  was  about  1000 
pounds.  Apart  from  the  construction  of  the  apparatus  the  yield  is 
influenced  by  the  current  density,  the  frequency  of  the  current,  gaseous 
pressure,  temperature  of  the  liquid  and  the  distance  between  consec- 
utive iron  plates.  If  the  reduction  is  not  pushed  beyond  a  point  cor- 
responding to  a  15  per  cent  decrease  in  the  iodine  number,  there  is 
a  complete  parallelism  between  the  decrease  in  the  iodine  number, 
increase  of  melting  point  and  absorption  of  hydrogen.  The  varia- 
tion of  the  iodine  number  or  the  increase  of  the  melting  point  per  unit 
of  electrical  energy  employed  is  taken  as  a  measure  of  the  trans- 
formation effected.  A  proportionality  between  the  quantity  of  sub- 
stance transformed  and  the  intensity  of  current  does  not  always  exist. 
For  a  given  intensity  of  current  the  quantity  transformed  reaches  a 
maximum  for  a  definite  distance  of  electrical  discharge;  this  maximum 
varies  with  the  pressure.  In  order  to  obtain  a  satisfactory  reaction 
the  current  must  act  simultaneously  on  both  liquid  and  gas.  Pro- 
longed action  of  the  current  causes  polymerization  and  the  reactions 
become  quite  complicated.  The  apparatus  can  be  used  for  deodoriz- 
ing fish  oil,  as  the  unsaturated  compounds  of  this  oil  take  up  hydrogen 
under  these  conditions.  Because  of  the  gradual  polymerization  pro- 
duced the  method  is  suggested  as  applicable  for  thickening  mineral 
oils  or  mixtures  of  mineral  oils  with  animal  or  vegetable  oils.  Molec- 
ular weights  as  high  as  2500,  as  determined  by  the  ebullioscopic 
method,  were  obtained.  The  viscosity  of  these  polymerized  oils  varies 
less  with  the  temperature  than  does  that  of  the  pure  mineral  oils ;  the 
coefficient  of  friction  of  the  former  is  also  stated  to  be  less. 

Apparatus  patented  by  Hemptinne  *  is  of  the  following  character: 
A  series  of  parallel  rotatable  metal  plates,  with  discs  of  insulating 
material  between  adjacent  plates,  is  arranged  within  a  fixed  casing 
or  within  a  vessel  that  rotates  with  the  plates  on  a  horizontal  axis. 

*  British  Patent  7101,  April  4,  1905. 


32 


THE  HYDROGENATION  OF  OILS 


Alternate  metal  plates  are  connected  to  one  pole,  and  the  remainder 
to  the  other  pole  of  a  source  of  electric  current,  in  order  to  establish  a 
silent  electric  discharge  between  the  plates.  The  latter  are  partially 
immersed  in  the  absorbing  liquid,  which  is  carried  around  by  small 
troughs  attached  to  the  casing  and  delivered  on  to  the  upper  portions 
of  the  plates,  so  that  a  thin  layer  of  liquid  is  maintained  on  the  plates, 
and  the  gas  to  be  treated  is  thus  brought  into  intimate  contact  with 
the  liquid.  An  electro-magnetic  device,  working  automatically,  main- 
tains a  constant  pressure  of  gas  in  the  apparatus  during  the  absorption.* 

A  process  for  the  production  of  neutral  hydrogenated  fats  from  raw 
material  containing  fatty  acid  involves  hydrogenating  the  oil  in  the 
presence  of  glycerine  under  which  condition  the  fatty  acids  are  claimed 
to  be  converted  into  glycerides.f 

With  an  apparatus  as  shown  in  Fig.  28,  Ellis  t  hydrogenates  by 
passing  a  current  of  oil  through  a  rotary  drum  containing  catalytic 


FIG.  28. 


material  supported  on  coarse  fragments  of  pumice,  so  that  on  rota- 
tion of  the  drum  the  catalyzer  moves  in  a  direction  substantially 
transversely  to  the  direction  of  the  oil  current.  Hydrogen  may  be 
passed  through  the  drum  as  a  counter-current.  A  given  quantity 
of  oil  may  be  circulated  in  this  manner  until  hardened  to  the  requisite 
degree. § 

*  The  application  of  the  electric  current  in  the  industry  of  oils  and  fats  has  been 
reviewed  by  Buttlar  (Chem.  Rev.  u.  d.  Fett  und  Harz  Ind.  (1912),  97)  who  discusses 
its  use  in  the  transformation  of  liquid  oils  into  solid  fats,  also  in  the  bleaching  of 
oils. 

t  Seifen.  Ztg.  (1913),  263. 

J  U.  S.  Patent  1,052,469,  Feb.  11,  1913. 

§  In  U.  S.  Letters  Patent  1,095,144  of  April  28,  1914,  to  Ellis  a  process  is  set 
forth  for  hardening  oils  which  involves  the  movement  of  oil  and  catalyzer  in  a  direc- 
tion transverse  to  that  of  the  hydrogen  current. 


CHAPTER  II 
METHODS   OF  HYDRO  GEN  ATION  — Continued 

Utescher  *  treats  oils  with  hydrogen  in  presence  of  a  finely-divided 
catalytic  agent,  and  at  the  same  time  the  material  is  subjected  to  the 
action  of  a  silent  electric  discharge. f  In  a  description  of  the  process, 
it  is  stated  that  the  "  silent  discharge"  is  prevented  from  coming  into 
actual  contact  with  the  fatty  substance,  only  chemically  active  rays 
(e.g.  from  a  mercury  vapor  lamp)  being  utilized.  It  is  also  stated 
that  the  process  may  be  effected  by  allowing  the  rays  to  impinge  on 
the  surface  of  a  catalytic  substance,  which  may  be  used  in  the  form 
of  plates. t 

The  joint  application  of  a  catalytic  and  an  electric  discharge  is 
claimed  to  give  a  greater  effect  than  either  agent  singly.  § 

Some  observations  on  the  effect  of  ultra-violet  light  on  catalytic 
action  have  been  made  by  Farmer  and  Parker  ||  which  indicate  that 
on  colloidal  platinum,  at  least,  the  ultra-violet  light  exerts  a  retarding 
influence  on  the  rate  of  catalytic  change.  Colloidal  platinum  was 
prepared  by  the  Bredig  method,  i.e.,  by  producing  an  arc  between 
platinum  electrodes  under  distilled  water.  Hydrogen  dioxide  was 
used  as  a  measure  of  catalytic  activity.  The  colloidal  platinum  was 
exposed  to  the  ultra-violet  light  and  samples  were  drawn  from  time 
to  time  in  order  to  get  exposures  of  varying  lengths,  the  samples  being 
introduced  into  hydrogen  peroxide  placed  in  an  apparatus  shown  in 
Fig.  29.  The  inclined  tube  of  this  apparatus  was  completely  filled 
with  dilute  hydrogen  peroxide  solution  and  a  bent  delivery  tube 
arranged  to  collect  any  liquid  displaced.  As  colloidal  platinum  breaks 

*  British  Patent  20,061,  Sept.  3,  1912. 

t  Hydrogen  activated  by  actinic  rays  is  used  for  oil  hardening  (Seifen.  Ztg.  (1913), 
1298). 

J  In  this  connection  it  is  noted  that  the  text  of  the  Utescher  specification  of 
German  Patent  266,662  of  1912  appears  in  Chem.  Rev.  u.  d.  Fett  u.  Harz  Ind.  (1913), 
308. 

§  Seifen.  Ztg.  (1913),  851.  F.  Gruner,  French  Patent  453,664,  Jan.  27,  1913.  Oils 
or  fats  are  subjected  to  the  action  of  a  silent  discharge  of  an  electric  current  of  very 
high  tension  and  frequency.  Currents  of  high  potential  (50,000  to  100,000  volts) 
and  high  frequency  are  employed. 

II  Jour.  Am.  Chem.  Soc.  (1913),  1524. 

33 


34 


THE  HYDROGENATION  OF  OILS 


FIG.  29. 


down  hydrogen  dioxide  yielding  oxygen,  the  evolution  of  the  gas  and 

consequent  displacement  of  liquid 
enabled  the  rate  of  decomposition 
to  be  measured. 

The  experiments  showed  that 
the  catalytic  activity  of  the  col- 
loidal platinum  was  almost  com- 
pletely destroyed  after  an  exposure 
of  six  hours,  the  activity  then  ob- 
served being  no  greater  than  that 
of  the  spontaneous  decomposition 
of  hydrogen  peroxide  itself.  It 
was  noted  that  the  light  caused 

the  platinum  to  be  precipitated  out  of  solution  as  a  black  flocculent 

material.     After  such  a  precipi- 
tation it  was  in  the  form  of  large 

mossy  clusters. 

While   no    observations   were 

made  with  respect   to  the   hy- 

drogenation  of  oils  under  these 

conditions,  in  view  of  the  action 

of  ultra-violet  light  on  solutions 

of  colloidal  platinum,  it  would 

appear    that    exposure    thereto 

may  be  expected  to  modify  the 

rate  of  reaction  in  the  harden- 
ing of  oils.* 

A    process   of    hydrogenating 

oils  involving  exposure  of  the  oil 

as  a  thin  film  on  a  web  carrying 

catalytic  material  has  been  pro- 
posed by  Walter.!   Fig.  30  shows 

one  form  of  apparatus  described 

by  Walter  for  carrying  out  this 

reaction.    A  is  a  closed  vessel  in 

which  is  placed  a  belt  or  web 

B  carrying  catalytic  material.     The  belt  may  be  made  of  asbestos 

or  cotton  cloth  and  may  be  impregnated  with   platinum,  iridium, 

*  Some  preliminary  experiments  by  the  author  point  to  a  reduction  in  the  iodine 
number  of  cottonseed  oil  when  exposed  to  ultra-violet  light  in  an  atmosphere  of 
hydrogen. 

t  Seifen.  Ztg.  (1913),  442. 


FIG.  30. 


METHODS  OF  HYDROGENATION 


35 


nickel  or  other  catalytic  material.  The  belt  is  carried  on  rollers  E, 
one  of  which  dips  into  the  oil.  Catalyzer  also  may  be  carried  in 
the  container  C  attached  to  the  belt  B.  D  is  a  steam  or  water  bath. 
H  is  an  inlet  and  F  an  outlet  for  hydrogen.  0  is  an  inlet  for  oil. 

Two  other  types  of  apparatus 
are  described:  one  consists  of  an 
upright  stationary  cylinder  jack- 
eted for  about  one-half  the  dis- 
tance. The  interior  has  a  shaft 
with  4  arms  upon  which  the 
catalyzer  is  carried  and  revolved 
through  the  liquid  and  gas.  A 
bucket  arrangement  is  also  at- 
tached to  the  shaft  to  throw 
liquid  upon  the  catalyzer.  An- 
other type  consists  of  a  jacketed 
horizontal  cylinder  with  a  rotating 
shaft  supporting  arms  for  carrying 

the  catalyzer.     (Figs.  31,  32  and  FlG  31 

33.) 

The  operation  may  be  carried  out  with  the  aid  of  chemically-active 
light  for  which  purpose  a  lamp-lighting  system  of  actinic  character 

is  shown  at  L  positioned  in  the 
receptacle  A.  Walter  lays  great 
stress  on  the  rapid  absorption  of 
hydrogen  by  oil  or  other  material 
exposed  in  this  manner  in  thin 
films.  He  states  that  although 
the  film  of  oil  on  the  belt  covers 
the  catalyzer,  and  in  consequence 
one  would  expect  the  reaction  to 
be  hindered  by  the  sealing  effect 
of  such  a  film,  yet  the  liquid  and 
gas  react  very  quickly  with  one 
another.  The  solubility  of  the  gas 
in  the  liquid,  as  well  as  the  physical 
properties  of  the  latter,  he  states, 
do  not  appear  to  play  any  essential 
part,  for  the  sparingly  soluble  hydrogen  exerts  its  reducing  action 
apparently  just  as  quickly  in  a  thinly-fluid  alcoholic  quinine  solution 
as  it  does  in  a  viscous  fish  oil. 

Walter  recommends  passing  the  oil  through  a  series  of  receptacles 


FIG.  32. 


36 


THE   HYDROGENATION  OF  OILS 


containing  catalyzer  attached  to  a  belt  as  described  or  to  an  agitator 
arm,  the  arrangement  being  such  that  the  oil  first  enters  the  receptacle 

which  contains  the  weakest  or  more  nearly 
spent  catalyzer  and  after  short  treatment 
passes  to  the  next  container  and  so  on  until 
finally  it  reaches  the  last  receptacle  where 
the  most  active  catalyzer  is  employed. 

In  connection  with  the  above  it  may 
be  stated  that  Walter  has  been  granted 
German  Patent  257,825,  of  July  27,  1911, 
which,  in  brief,  has  to  do  with  the  produc- 
tion of  chemical  reactions  between  liquids 
and  gases  under  the  influence  of  a  contact 
substance  or  of  chemically-active  rays. 
Porous  or  roughened  bodies,  which  may 
serve  as  contact  substances,  are  supported 
on  movable  carriers  and  are  caused  alter- 
nately to  dip  into  the  liquid  and  then  rise 
into  the  gas  above  the  liquid,  so  as  to 
bring  fresh  quantities  of  the  liquid  con- 
tinually into  contact  with  the  gas,  over  a 
large  surface.  Several  reaction  chambers 
through  which  the  gas  and  liquid  pass  in 
a  definite  order  are  preferably  used.  In 
some  respects  this  resembles  the  process 
of  Kayser  previously  discussed. 

Birkeland  and  Devik  *  employ  a  form  of  apparatus  which  permits 
of  forcing  a  mixture  of  oil  and  catalytic  agent  downwards  through  a 
nozzle  into  an  atmosphere  of  hydrogen,  filling  the  space  above  the 
bulk  of  the  oil,  which  is  contained  in  an  autoclave.  The  hydrogen 
is  drawn  into  the  oil  jets  by  injector  action  and  subsequently  rises  in 
small  bubbles  through  the  body  of  oil.  The  process  is  preferably 
carried  out  under  a  pressure  of  10  to  15  atmospheres  and  at  a  tem- 
perature of  about  150°  C.  Sudden  reduction  of  the  pressure  is  claimed 
to  promote  the  hydrogenation  of  the  oil. 

Brochet  f  treats  unsaturated  compounds  as  a  class,  by  hydrogen, 
in  the  presence  of  a  catalyst.  Hydrogen  or  a  gaseous  mixture  con- 
taining hydrogen  is  passed  into  the  substance  to  be  treated,  either  in 
the  liquid  form  or  in  solution  or  suspension,  in  presence  of  a  base- 


FIG.  33. 


*  French  Patent  456,632,  April  14,  1913. 
t  French  Patent  458,033,  July  27,  1912. 


METHODS  OF  HYDROGENATION  37 

metal  catalyst,  which  may  be  held  on  an  inert  support.  The  velocity 
of  the  reaction  is  increased  by  working  under  pressure,  although 
extremely  high  pressures  are  not  necessary.  By  this  procedure  various 
unsaturated  organic  compounds  may  be  made  to  combine  with 
hydrogen.* 

A  somewhat  elaborate  gas-measuring  system  has  been  proposed  by 
deKadt.f  The  amount  of  gas  absorbed  by  a  liquid  or  other  material 
in  a  closed  vessel,  for  example,  in  the  combination  of  hydrogen  with 
fats  or  oils  in  the  presence  of  a  catalyst,  is  determined  by  means  of  a 
gas  meter  or  other  measuring  instrument  arranged  on  the  pipe  sup- 
plying the  gas  and  adapted  to  cut  off  the  supply  when  a  certain  amount 
of  gas  has  been  supplied  or  combined.  When  apparatus  is  used  in 
which  the  gas  is  introduced  through  a  fine-spray  nozzle  at  the  bottom 
of  the  liquid,  and  unabsorbed  gas  from  the  top  of  the  vessel  is  with- 
drawn and  again  introduced  into  the  liquid,  two  meters  are  fitted  upon 
the  inlet  and  outlet  pipes  respectively  so  as  to  act  differentially  upon 
an  indicator  needle  which  thus  records  the  difference  between  the 
volume  of  gas  supplied  and  the  volume  unabsorbed.  The  needle 
may  control  an  electric  contact  by  which  the  gas  supply  is  shut  off 
and  the  circulating  pump  stopped  as  soon  as  the  requisite  amount  of 
gas  has  been  absorbed. 

Fig.  34  shows  the  deKadt  system. 

The  reaction  vessel  1  is  connected  at  its  upper  part  through  a  suitable  pipe  con- 
nection 2  with  a  suction  and  force  pump  3.  At  one  part  of  its  length  this  pipe  con- 
nection 2  is  formed  into  a  cooling  coil  4,  which  is  located  in  a  water  reservoir  5.  At 
the  lower  part  of  the  reaction  vessel  1  a  nozzle  or  rose  head  6  is  provided,  and  from 
this  nozzle  a  pipe  7  leads  to  the  vessel  8  containing  the  hydrogen.  This  hydrogen- 
containing  vessel  communicates  with  the  pump  3  by  means  of  a  pipe  9  and  contains 
a  cooling  coil  12  provided  with  inlets  and  outlets  for  the  supply  and  discharge  of 
the  cooling  water. 

The  material  to  be  treated,  such  as  fats  or  oils,  and  the  catalytically  acting  sub- 
stances are  supplied  to  the  reaction  vessel  through  a  charging  door  14.  In  the  first 
place  the  hydrogen  supply  pipe  7  is  cut  off  from  the  reaction  vessel  1  and  the  pipe  9, 
connecting  the  hydrogen-containing  vessel  with  the  pump,  is  closed  by  a  cock  15. 
The  materials  contained  in  the  reaction  vessel  are  then  heated  by  means  of  a  steam 
jacket  or  steam  coil,  and  the  air,  contained  in  this  vessel,  is  exhausted  by  means  of 
the  pump  3  and  escapes  to  the  atmosphere  by  way  of  the  cock  16,  the  cocks  18 
and  17  being  open  for  this  purpose.  Hydrogen  is  then  supplied  through  a  pipe 
connected  with  the  pump  3  and  is  forced  into  the  hydrogen-containing  vessel  8 
through  the  pipe  9,  the  cocks  17  and  15  being  open.  When  the  necessary  tension 
has  been  attained,  the  cocks  15  and  17  in  the  hydrogen  supply  pipe  are  closed  and 
the  cock  24  at  the  upper  part  of  the  reaction  vessel  connecting  the  vessel  and  pipe  2 
are  opened.  A  valve  19  is  arranged  in  the  pipe  connecting  the  hydrogen  vessel  with 

*  See  also  First  Addition  dated  Oct.  8,  1912. 
t  British  Patent  5773,  March  7,  1912. 


38 


THE  HYDROGENATION  OF  OILS 


the  lower  part  of  the  reaction  vessel  by  opening  said  valve  19,  behind  which  a 
reducing  valve  20  is  arranged;  the  hydrogen  is  conducted  by  the  pipe  7  into  the 
vessel  1,  where  it  passes  from  the  nozzle  6  through  the  material  to  be  treated  with 
which  it  combines  to  some  extent,  while  the  excess  escapes  upwards  and  is  again 
forced  into  the  hydrogen-containing  vessel  8  by  the  pump  3,  the  cocks  being  suitably 
adjusted.  The  supply  of  hydrogen  contained  in  the  vessel,  which  is  not  supple- 
mented by  a  fresh  external  supply  during  the  chemical  reaction,  must  gradually 
decrease  in  tension  owing  to  the  combination  with  the  contents  of  the  reaction 
vessel.  This  decrease  in  tension  can  be  utilized  empirically  for  determining  the 
progress  of  the  chemical  reaction  or  for  ascertaining  its  various  stages  or  its  com- 
pletion. These  indications  would,  however,  only  be  approximate  and  deKadt 
therefore  provides  means  to  interrupt  the  supply  of  hydrogen  to  the  reaction  vessel 
automatically  after  the  consumption  of  the  necessary  quantity  of  combined  hy- 


FIG.  34. 

With  this  object  a  gas  meter  21  is  arranged  on  the  pipe  7  supplying  the  hydrogen 
to  the  reaction  vessel  and  indicates  the  quantity  of  hydrogen  passing  from  the 
container  8  into  the  reaction  vessel  1.  A  similar  meter  22  is  arranged  on  the 
return  pipe  2  and  measures  the  quantity  of  gas  being  withdrawn.  Both  these 
meters  act  on  an  indicating  shaft  23  in  such  a  manner  that  by  the  rotation  of  the 
shaft  the  first  gas  meter  21  moves  the  hand  of  indicating  shaft  23  upwards,  while 
the  other  gas  meter  22  moves  it  rearwards  so  that  the  index  hand  shows  the  differ- 
ence, that  is  to  say  the  consumption  of  hydrogen.  An  electric  contact  is  arranged 
in  the  path  of  the  index  hand  and  when  it  reaches  a  certain  position,  in  which  the 
necessary  quantity  of  kydrogen  has  been  consumed,  the  circuit  is  closed,  and  the 
hydrogen  supply  is  cut  off. 

In  hydrogenating  oils  containing  the  hydroxyl  group,  at  high  tem- 
peratures, this  group  is  destroyed  and  Markel  and  Crosfield  *  propose 

*  British  Patent  13,519,  June  6,  1911. 


METHODS  OF  HYDROGENATION  39 

the  preparation  of  saturated  hydroxy-fatty  acids  and  their  glycerides 
by  treating  the  corresponding  unsaturated  acids  or  glycerides  with 
hydrogen  in  the  presence  of  a  catalyst  other  than  palladium  and  pal- 
ladium hydroxide,  at  as  low  a  temperature  as  possible,  preferably 
just  above  the  melting  point  of  the  final  product,  in  order  to  avoid 
splitting  off  of  the  hydroxyl  group  or  to  control  such  splitting  to  any 
desired  extent.  Suitable  catalysts  recommended  are  iron,  nickel, 
cobalt,  copper,  etc.,  also  oxides,  hydroxides  and  salts,  which  may  be 
deposited  upon  suitable  supports,  preferably  finely  divided.  As  raw 
materials  the  mixture  of  unsaturated  acids  obtained  by  treatment  of 
oleic  acid  with  sulfuric  acid,  the  oxidation  products  of  linseed,  cot- 
tonseed and  rape  oils,  also  castor,  grape  seed  and  whale  oils  may  be 
used. 

Temperature  of  Hydrogenation.  For  each  compound  there  usually 
exists  a  well-defined  range  of  temperature  within  which  hydrogen  is 
effectively  added.  Somewhere  in  this  temperature  interval  lies  the 
mean  effective  temperature,  that  is  the  temperature  of  maximum  sat- 
uration velocity.  For  a  number  of 'fatty  oils  this  approximates  180°  C. 
or  356°  F.  with  a  nickel  catalyzer.  As  a  rule  hydrogenation  is  accel- 
erated more  by  a  given  temperature  rise  from  below  the  mean  effective 
temperature  than  the  same  temperature  increase  above  this  point  re- 
tards the  reaction.  For  example,  raising  the  temperature  from  170° 
to  180°  C.  increases  the  rate  of  hydrogen  addition  in  a  certain  measure 
while  elevating  the  temperature  from  180°  to  190°  C.  retards  the  rate, 
but  to  a  lesser  degree  for  such  10-degree  temperature  increment  than 
the  previous  increase  in  the  rate.  In  operation  on  the  large  scale  it 
is,  therefore,  better  to  err  by  maintaining  the  oil  slightly  above  rather 
than  below  the  mean  effective  temperature,  unless  of  course  a  lower 
temperature  is  prescribed  because  of  the  character  of  the  oil.  Rapidity 
of  treatment  often  is  desired  especially  in  edible  oils  where  protracted 
contact  with  the  catalyzer  introduces  the  danger  of  solution  of  the 
metallic  material  in  the  oil  to  an  objectionable  degree.* 

The  range  of  temperature  mentioned  above  varies  with  each  type 
of  catalyzer.  Platinum  and  palladium,  at  least  in  certain  forms,  may 
be  used  at  temperatures  between  80°  and  100°  C. ;  nickel  between 
160°  to  200°  C. ;  nickel  oxide  and  copper  at  about  200°  C.  and  upwards; 

*  The  hydrogenation  of  unsaturated  compounds,  particularly  fatty  acids  and 
their  glycerides,  into  saturated  compounds  by  hydrogen  in  the  presence  of  finely- 
divided  metal,  according  to  Higgins  is  accelerated  by  the  presence  of  formic  acid 
or  other  volatile  organic  acid.  The  formic  acid  may  be  carried  by  the  hydrogen, 
or  the  acid  mixed  with  the  material  before  treatment.  (Chem.  Abs.  (1914), 
437.) 


40  THE  HYDROGENATION  OF  OILS 

all  depending  on  the  physical  and  chemical  constitution  of  the  catalytic 
material.* 

Caro  f  considers  the  presence  of  carbon  monoxide  in  hydrogen  used 
for  hardening  fats  with  nickel  catalyzers  to  be,  under  some  circum- 
stances, injurious  to  the  catalyzer.  Maintaining  the  temperature  of 
the  oil  during  hydrogenation  above  200°  C.  is  said  to  be  beneficial  as 
any  nickel  carbonyl  formed  will  be  at  once  decomposed  at  that  tem- 
perature. The  hydrogenation  of  many  substances  under  these  con- 
ditions is  not  feasible  and  Caro  recommends  that  the  gas  first  be  passed 
over  nickel  at  180°  C.  to  convert  the  carbon  monoxide  into  methane, 
which  is  inert. 

DeKadt  |  saturates  fatty  acids  or  their  esters  with  hydrogen  by  the 
use,  as  a  catalyzer,  of  a  soap  of  a  heavy  or  noble  metal,  formed  from 
a  fat  or  fatty  acids,  whose  melting  point  lies  above  that  of  the  sub- 
stance to  be  treated.§ 

It  is  claimed  by  Fuchs  ||  that  his  investigations  have  shown  the 
present  methods  of  reduction  for  the  most  part  are  improperly  founded, 
causing  long  duration  of  time  of  treatment  coupled  with  marked  loss 
of  hydrogen  and  heat;  use  of  a  great  excess  of  hydrogen  or  catalyzer; 
injurious  action  of  the  long  heating  on  the  color,  taste  and  odor  of 
the  reduced  fat;  and  the  application  of  high  pressure  in  apparatus 
which  involves  costly  autoclaves,  dangerous  to  handle.  Fuchs  de- 
clares th#t  the  conduct  of  reduction  of  fatty  bodies  is  essentially 
improved  if  the  following  theoretical  conditions  are  observed: 

(1)  Thermal  considerations:  A  quickening  of  the  reaction  is  ob- 
tained when  the  oil  to  be  treated  is  maintained  at  only  a  moderate 
temperature  (0°  to  150°  C.),  while  the  hydrogen  employed  is  heated 
to  200°  to  250°  C.  The  avoidance  of  strong  heating  of  the  oil  which 
is  being  treated  is  favorable  to  the  quality  of  the  final  product,  while 
preheating  the  hydrogen  appears  to  increase  its  activity.  Compara- 
tive tests  show  that  in  this  way  the  speed  of  the  reaction  can  be  in- 
creased by  about  10  per  cent.  For  preheating  the  current  of  gas, 
copper  or  nickel  coils  in  an  oil  bath  are  used.  The  oil  bath  may  be 

*  Ipatiew  (Chem.  Ztg.,  1914,  374)  has  noted  that  the  hydrogenation  of  fatty 
acids  with  metallic  nickel  begins  at  150°  C.  and  with  nickel  oxide  at  230°  C.  The 
reaction  progresses  readily  at  both  high  and  low  pressures. 

t  Seifen.  Ztg.  (1913),  852. 

t  Chem.  Ztg.  Rep.  (1913),  541,  British  Patent  18,310,  Aug.  9,  1912. 

§  Utescher  (Seifen.  Ztg.  (1912),  1044)  discusses  from  the  patent  point  of  view  the 
claims  made  by  deKadt  in  Seifen.  Ztg.  (1912),  960;  see  also  Seifen.  Ztg.  (1912),  900 
and  1008. 

II  Seifen.  Ztg.  (1913),  982.  Reduction  of  unsaturated  fatty  acids  and  their 
glycerides,  Belgium  Patent  256,574,  1913. 


METHODS  OF  HYDROGENATION  41 

maintained  at  the  requisite  temperature  through  circulation  of  oil 
heated  at  a  distant  point. 

(2)  Chemical  considerations:  Since  it  is  impossible  to  have  free 
hydrogen  in  its  most  active  form,  that  is,  in  a  nascent  state,  act  upon 
the  oil  to  be  treated,  because  the  quality  of  the  oil  is  injured,  Fuchs 
observes  that  means  must  be  provided  to  apply  the  hydrogen  in 
the  atomic  form.  This  can  be  carried  out  through  the  application 
of  chemically  active  rays.  Dissociation  of  the  hydrogen  molecule 
appears  also  to  occur  when  molecular  hydrogen  is  passed  over  cata- 
lytic material  such  as  palladium  black  or  freshly  prepared  nickel 
powder  and  then  is  allowed  to  diffuse  under  high  pressure  through 
heated  plates  of  metal.  The  activity  of  the  dissociated  hydrogen, 
it  is  claimed,  is  from  15  to  20  per  cent  higher  than  the  normal  gas. 
The  catalytic  material  may  be  placed  in  a  tube  of  suitable  length  or 
on  the  plates  of  a  column  apparatus.  By  way  of  illustration  Fuchs 
states  that  cottonseed  oil  carrying  0.9  per  cent  of  a  catalyzer,  prepared 
from  nickel  carbonate,  is  raised  to  a  temperature  of  120  degrees  and 
is  subjected  to  hydrogen  under  a  pressure  of  18  atmospheres,  the  gas 
having  been  chemically  activated  by  passage  through  an  iron  tube 
3  meters  in  length  and  60  mm.  in  diameter,  lined  with  platinized 
asbestos  and  heated  to  250°  C.  In  this  way  by  two  hours'  treatment 
a  fatty  body  having  a  melting  point  of  44°  C.  was  prepared.  In  three 
hours  a  fat  melting  at  65.4°  C.  was  obtained.  Fuchs  notes  that  ordi- 
narily from  5  to  8  hours  would  be  required  to  secure  such  products. 
The  claims  of  Fuchs'  Patent  call  for  the  reduction  of  unsaturated 
fatty  acids  and  their  glycerides  by  means  of  hydrogen  according  to 
the  contact  process,  wherein  strongly  heated  hydrogen  is  caused  to 
react  on  only  moderately  heated  oil;  also  the  treatment  of  oil  with 
atomic  hydrogen  whose  activity  has  been  increased  by  treatment  with 
chemically  active  rays. 

The  employment  of  nickel  carbonyl  by  Shukoff  has  been  described 
in  the  foregoing.  In  a  somewhat  similar  manner  Lessing  *  makes  use 
of  a  mixture  of  hydrogen  and  a  gaseous  metallic  compound  brought 
into  contact  with  the  substance  under  suitable  conditions  of  tempera- 
ture and  pressure.  Lessing  states  he  has  found  that  a  great  number 
of  substances  may  be  hydrogenated  by  treating  them  at  elevated 
temperatures  with  hydrogen  to  which  a  metallic  carbonyl  vapor,  or 
gas  containing  a  metallic  carbonyl,  has  previously  been  added;  or 
with  a  mixture  of  gases,  containing  hydrogen  in  which  metal  carbonyl 
has  been  formed  by  combination  of  carbon  monoxide,  originally  in 
the  mixture,  with  a  metal.  The  rapidity  with  which  the  hydrogena- 
*  British  Patent  18,998,  1912. 


42  THE  HYDROGENATION  OF  OILS 

tion  proceeds  under  these  conditions  may  be  explained  as  the  effect 
of  the  liberation  of  elementary  metal,  the  properties  of  which  "  in 
statu  nascendi  "  are  known  to  be  very  different  from  those  of  metal 
which  is  merely  finely  subdivided.  Lessing  observes  that  it  has 
already  been  proposed  to  use  as  the  catalyzer  finely-subdivided  nickel, 
made  by  decomposing  nickel  carbonyl  in  the  heated  material  prior 
to  the  introduction  of  the  hydrogenating  gas,  but  it  was  not  known 
that  technical  advantages  accrue  from  conveying  the  nickel  carbonyl 
into  the  material  simultaneously  with  the  hydrogenating  agent  so 
that  elementary  liberation  of  nickel  occurs  in  close  contact  with  hydro- 
gen and  the  substance  to  be  hydrogenated.  These  advantages  are 
that  the  proportion  of  catalyzer  is  very  much  reduced  and  the  reaction 
proceeds  much  more  rapidly.  Lessing  carries  out  his  process  in 
various  ways.  It  is  convenient  to  introduce  nickel  carbonyl  into  the 
hydrogen  gas  by  passing  a  mixture  of  the  latter  with  carbon  monoxide 
over  reduced  nickel  in  the  well-known  manner  for  making  nickel 
carbonyl. 

The  mixture  of  gases  employed  need  not  be  of  great  purity  and  may  be  made  from 
water-gas,  or  by  the  thermal  decomposition  of  coal  gas  or  of  coke-oven  gas  or  of 
hydrocarbons  of  any  kind,  but  best  results  are  obtained  when  the  amount  of  carbon 
monoxide  in  the  gases  is  limited  to  that  requisite  for  forming  the  nickel  carbonyl 
necessary  for  the  reaction,  and  in  any  case  the  proportion  of  carbon  monoxide  in 
the  mixture  should  not  exceed  25  per  cent.  For  example,  when  an  oil  such  as  a 
glyceride  or  a  fatty  acid  is  being  hydrogenated,  the  simplest  mode  of  operating  con- 
sists in  passing  hydrogen  containing  5  to  10  per  cent  of  carbon  monoxide  first  through 
a  volatilizer  charged  with  reduced  nickel  and  then  through  the  oil  contained  in  a 
closed  vessel  heated  to  a  suitable  temperature,  say  from  200°  to  240°  C.  The  gases 
passing  away  from  the  vessel  are  returned  to  the  volatilizer  to  be  used  again,  hydro- 
gen or  a  gas  rich  therein  being  added  to  compensate  for  that  absorbed  by  the  oil. 
The  proportion  of  nickel  required  for  the  hydrogenation  is  very  small;  under  proper 
conditions  excellent  results  can  be  obtained  with  a  proportion  equivalent  to  0.1  part 
of  nickel  to  100  parts  of  oil. 

Another  mode  of  operating  consists  in  forcing  the  substance  to  be  treated,  if  it 
is  in  a  liquid  form,  through  spraying  nozzles  into  a  gas-tight  vessel  which  may  be 
suitably  heated  to  the  temperature  most  favorable  to  the  catalytic  hydrogenation 
of  the  substance.  Into  the  same  container,  preferably  at  or  near  the  bottom,  hydro- 
gen gas  containing  metal  carbonyl,  for  instance  nickel  carbonyl,  is  passed.  The 
excess  of  gases  leaves  the  vessel  through  an  outlet  at  the  upper  part  and  may  be 
returned  into  the  gas  circuit  after  the  products  carried  with  it  have  been  separated 
by  condensing  or  washing.  The  treated  liquid  may  be  drained  off  and  returned  to 
the  reaction  vessel  until  hydrogenation  has  proceeded  far  enough.  Instead  of  heat- 
ing the  reaction  vessel,  or  in  addition  to  doing  so,  the  liquid  may  be  preheated  in 
a  suitable  apparatus,  before  entering  the  vessel,  to  a  temperature  required  for  the 
reaction. 

By  another  method  of  carrying  out  the  process,  a  solution  of  metal  carbonyl  in 
oil  is  prepared,  which  may  be  accomplished  by  passing  the  gas  carrying  nickel  car- 


METHODS  OF  HYDROGENATION  43 

bonyl  through  cold  oil.     This  solution  is  forced  through  a  spray  nozzle  into  a  heated 
vessel  where  it  meets  hydrogen  whereupon  hydrogenation  occurs. 

If  the  compound  to  be  treated  is  in  the  state  of  gas  or  vapor,  as  for  instance  in 
the  hydrogenation  of  the  more  volatile  tar  oils,  it  is  simply  mixed  with  hydrogen 
containing  the  nickel  carbonyl  and  is  subjected  to  the  temperature  required  for 
hydrogenation.  Likewise  in  the  case  of  a  liquid  some  hydrogen  may  be  mixed  with 
the  liquid,  the  spray  being  then  preferably  formed  by  injector  action  instead  of  by 
liquid  pressure. 

The  use  of  nickel  carbonyl  for  the  production  of  catalytic  material 
also  has  been  patented  by  Kamps,*  who  introduces  the  carbonyl  into 
an  autoclave  at  a  temperature  above  43°  C.  and  a  pressure  of  751  mm., 
and  the  oil  which  is  to  be  reduced  is  maintained  under  such  pressure 
and  temperature  conditions  that  the  decomposition  of  the  nickel 
carbonyl  is  brought  about.  At  60°  C.  the  oil  should  be  under  a 
pressure  of  less  than  2  atmospheres  and  at  180°  C.  less  than  30  at- 
mospheres. 

Another  method  of  utilizing  nickel  carbonyl  for  the  production  of 
catalytic  material  is  that  proposed  by  the  Bremen  Besigheimer 
Olfabriken  f  according  to  which  method  kieselguhr  or  similar  porous 
material  is  saturated  with  nickel  carbonyl  and  the  material  is  heated 
to  cause  the  deposition  of  metallic  nickel  on  the  carrier.  The  nickel- 
containing  powder  is  immediately  ground  with  oil  to  form  a  paste- 
like  mass,  this  operation  being  carried  out  with  the  exclusion  of  air. 
It  is  also  stated  that  the  contact  material  may  be  reworked  in  the 
following  manner: 

It  is  first  purified  by  extraction,  the  nickel  removed  and  after  con- 
version of  the  latter  into  a  pulverulent  form  is  again  used  for  the 
production  of  nickel  carbonyl.  It  is  recommended  that  the  carbon 
monoxide  obtained  by  the  Linde-Caro  process  in  the  liquefaction  of 
water  gas  be  used  for  the  production  of  the  carbonyl. 

^A  form  of  apparatus  adapted  to  be  used  in  carrying  out  a  process 
of  hydrogenating  oils  J  which  relates  more  specifically  to  the  treat- 
ment of  rancid  oils  or  oils  of  high  acidity  is  shown  in  Fig.  35.  An 
oil  containing  a  high  proportion  of  free  fatty  acids  or  products  of 
rancidification  may  be  diluted  with  a  neutral  oil  and  the  mixture 
hydrogenated  to  a  hard  fat,  although  the  original  rancid  oil  be  in- 
capable of  hydrogenation,  because  of  its  poisoning  action  on  catalyzers. 
The  apparatus  consists  of  a  tank  having  a  dome  in  which  atomizers 
are  mounted  and  by  which  the  oil  is  atomized  with  hydrogen  gas,  and 
is  then  allowed  to  trickle  through  a  series  of  screens  placed  in  the  lower 

*  Belgium  Patent  246,975. 

t  Zeit.  f.  angew.  Chem.  (1913),  ref.  627. 

t  Ellis,  U.  S.  Patent  1,078,136,  Nov.  11,  1913. 


44 


THE  HYDROGENATION  OF  OILS 


part  of  the  dome.  Palm  oil  may  be  heated  without  access  of  air  to  a 
temperature  at  which  its  color  is  destroyed  by  hydrogenating  under 
these  conditions,  producing  a  fat  which  is  especially  useful  to  soap 
makers. 

A  process  for  thickening  oilsand  fats  is  described  by  Scherieble.* 
The  material  to  be  treated  is  subjected  to  ozone-forming  electric 

discharges  by  sending  such  dis- 
charges directly  through  it. 
Potentials  of  10,000  to  20,000 
volts  yield  no  results,  as  oils  and 
fats  introduced  between  the  elec- 
trodes impede  any  discharge  by 
reason  of  their  great  insulating 
properties.  Experiments  in  this 
direction  have,  however,  shown 
that  discharges  through  oils  and 
fats  are  quite  possible  when  high 
potentials  of  50,000  to  100,000 
volts  and  beyond  are  employed. 
The  higher  the  potential  of  the 
electric  current  and  the  greater 
its  frequency  the  easier  it  is  to 
pass  a  discharge,  with  the  for- 
FIG.  35.  mation  of  ozone,  through  thick 

layers  of  oil. 

The  oil  5  to  be  thickened  or  bleached  is  placed  in  the  pan  6  (Fig.  36), 
the  bottom  of  which  forms  one  electrode,  connected  to  the  source  of 
electricity  by  the  conductor  shown. 
The  second  electrode  8  having  the 
terminal  points  9  and  fed  through 
the  conductor  10  is  placed  above 
the  oil  so  that  the  discharge  11 
acts  upon  the  oily  material. 

By  the  Calvert  system  the  oil 
is  submitted  to  violent  agitation 
while  under  a  hydrogen  pressure  FlG  36 

of  250  pounds  per  square  inch  and 

at  a  temperature  of  180°  to  200°  C.,  in  a  specially  constructed  auto- 
clave having  an  electric  motor  (for  stirring)  enclosed  in  a  chamber 
which  is  under  the  same  hydrogen  pressure  as  the  autoclave  proper. 


*  U.  S.  Patent  1,079,727,  Nov.  25,  1913. 


METHODS  OF  HYDROGENATION 


45 


The  motor  chamber  is  substantially  an  extension  of  the  autoclave, 
but  is  so  far  removed  from  the  latter  as  to  be  unaffected  by  the  heat. 

The  annexed  illustration,  Fig.  37,  represents  this  type  of  oil  hydro- 
genating  apparatus  which  the  Metropolitan  Laboratories  have  put 
on  the  market.  In  the  design  is  embodied  the  patented  principle  of 
enclosing  the  agitating  motor  in  a  chamber  essentially  an  extension  of 
the  autoclave  proper,  and  under 
the  same  gas  pressure.  By  this 
arrangement  the  risk  of  leakage 
is  entirely  eliminated,  and  at 
the  same  time  high  stirring 
speeds  are  rendered  possible 
without  the  frictional  resistance 
which  would  be  caused  by  shafts 
passing  through  glands,  etc. 
The  autoclave  proper  is  the 
lower  vessel  shown  in  the  illus- 
tration, and  is  enclosed  in  a 
heat-insulating  jacket.  The  top 
vessel  contains  the  electric 
motor,  the  intermediate  tube 
through  which  the  stirrer  shaft 
passes  being  enclosed  in  a  water 
jacket  in  the  larger  sizes.  Cur- 
rent is  conveyed  to  the  motor 
by  insulated  screws  on  the  top 
of  the  machine.  On  the  right 

is  the  flue  and  the   hydrogen  pIG  37 

feed    pipe,    the    charging    and 

discharging  tube  being  shown  on  the  left.  For  convenience  in  dis- 
charging the  contents,  in  the  smaller  sizes  the  whole  is  mounted  on 
trunnions. 

The  oil  is  brought  into  a  state  of  fine  division  by  the  stirrer  blades, 
which  cause  the  liquid  to  rotate  against  the  inner  side  of  the  vessel, 
to  which  perforated  baffle  plates  are  fitted.  The  working  pressure  is 
200  to  250  pounds  per  square  inch,  and  the  temperature  about  185°  C., 
but  every  machine  is  tested  to  1000  pounds  cold  water  and  to  500 
pounds  gas  at  200°  C.  The  illustration  represents  a  small  size,  suit- 
able for  oil  laboratories,  which  stands  about  4  feet  high,  but  large 
units  are  also  manufactured  for  working  in  batteries  on  a  commercial 
scale.* 

*  Chem.  Trade  Jour.  (1913),  618. 


46 


THE  HYDROGENATION  OF  OILS 


An  apparatus  for  hardening  oil,  proposed  by  Wilbuschewitsch,* 
comprises  the  vessel  R  (Fig.  38)  containing  the  fat  to  be  treated  and 
the  vessel  0  containing  the  catalyst.  Differentially-connected  pumps 
A  A'  feed  the  oil  and  the  catalyst  into  the  mixing  device  B  in  which  an 
intimate  mixture  of  the  oil  and  the  catalyst  is  obtained.  This  mixture 
passes  through  a  pipe  G  and  the  valve  H  into  an  autoclave  J'  which  is 
provided  with  a  spraying  device  C"  consisting  of  a  number  of  spraying 
.nozzles  so  arranged  that  the  oil  and  catalyst  are  uniformly  scattered 


FIG.  38. 


in  finely-subdivided  condition  throughout  the  whole  inner  space  of 
the  autoclave.  A  compressor  K  forces  hydrogen  into  the  autoclave 
under  a  pressure  of  about  9  atmospheres.  The  pipe  X  extends  from 
the  upper  part  of  the  autoclave  downward  to  the  lower  end  of  the 
same  and  is  provided  at  its  lower  end  in  the  conical  lower  part  of  the 
autoclave  with  an  admission  nozzle  Df.  By  this  spraying  system  an 
intimate  contact  of  the  oil  mixture  with  the  hydrogen  is  achieved  on 
the  counter-current  principle.  The  autoclave  is  heated  to  between 
100°  to  160°  C.  according  to  the  nature  of  the  oil  under  treatment. 
The  reduction  by  the  hydrogen  begins  at  the  upper  part  of  the  auto- 
clave. The  partially  reduced  oil  mixture  collects  in  the  conical  part 
of  the  autoclave  and  is  sprayed  in  the  form  of  a  fountain  through  the 
autoclave  by  the  incoming  hydrogen.  The  mixture  is  forced  by  pump 
Ef  into  the  second  autoclave  J2.  The  hydrogen  enters  this  autoclave 
through  pipe  Y  and  the  action  of  the  first  autoclave  is  repeated.  Any 

*  U.  S.  Patent  1,079,278,  Nov.  18,  1913. 


METHODS  OF  HYDROGENATION  47 

number  of  such  autoclaves  can  be  arranged  in  series  or  parallel  to  each 
other  in  accordance  with  the  extent  of  .reduction  required.  It  is 
generally  suitable  to  use  one  autoclave  for  each  increase  of  melting 
point  by  15°  C.  When  the  fat  has  attained  the  desired  melting  point 
which  is  ascertained  by  samples  withdrawn  from  the  autoclaves,  the 
oil  mixture  is  withdrawn  through  the  valve  U  into  the  centrifugal 
apparatus  F.  Here  the  oil  is  separated  from  the  catalyst.  The 
finished  reduced  oil  flows  into  the  reservoir  N  while  the  catalyst  is 
returned  through  the  pipe  R'  and  valves  S  and  T  to  the  vessels  0  and 
P.  At  first  when  the  catalyst  which  Wilbuschewitsch  employs  is 
still  quite  fresh,  he  states  that  only  a  little  of  it  is  necessary  —  1  per 
cent  may  be  advantageously  used.  When,  however,  in  the  course  of 
the  operation  its  catalytic  power  decreases,  correspondingly  more  of 
it  must  be  used.  The  regulation  of  the  quantity  of  catalyst  may  be 
attained  by  a  suitable  adjustment  of  the  differential  pump  system. 
When  the  catalyst  is  completely  spent  it  is  allowed  to  flow  out  through 
the  valve  S  into  the  reservoir  P  in  order  to  be  regenerated.  The 
working  is  continued  by  introduction  of  fresh  catalyst  through  the 
valve  T.  The  hydrogen  not  consumed  passes  through  the  check 
valve  W  and  pipe  Q  and  cooling  worm  L  into  a  vessel  M  filled  with 
caustic  soda  lye  where  it  is  purified  and  then  passes  to  the  compressor 
and  autoclaves. 

*  Wimmer  and  Higgins  *  use  as  catalyzers  organic  metal  salts  such 
as  the  formates,  acetates  or  lactates  of  copper,  iron,  nickel  or  cobalt. 
These  require  no  special  preparation  before  their  use  as  catalytic 
agents;  and  it  is  claimed  that  impurities  contained  in  the  reducing 
gas  employed  in  the  treatment  do  not  render  these  compounds  in- 
effective. Wimmer  and  Higgins  state  that  those  processes  in  which 
finely-divided  metals  are  employed  in  the  treatment  of  unsaturated 
compounds  call  for  the  employment  of  intense  mechanical  agitation 
to  obtain  admixture  of  the  catalysts  and  the  liquid,  or  require  the 
distribution  of  the  metal  over  the  outer  surface  of  contact  carriers  such 
as  pumice  stone,  kieselguhr,  etc.  By  their  process  the  compound  to 
be  reduced  is  mixed  with  the  organic  metallic  salt,  heated  to  a  suitable 
temperature,  and  either  a  stream  of  the  reducing  gas  is  passed  through 
the  mixture,  or  the  latter  is  subjected  to  an  atmosphere  of  the  gas  in 
a  closed  vessel,  while  contact  between  the  gas  and  the  mixture  or 
emulsion  may  be  assisted  by  agitation.  Under  these  conditions  the 
saturation  is  said  to  take  place  comparatively  quickly  and  the  spent 
or  partly  spent  catalytic  agent  can  be  removed  by  simple  filtration 
after  the  operation. 

*  U.  S.  Patent  1,081,182,  Dec.  9,  1913. 


48 


THE  HYDROGENATION  OF  OILS 


According  to  an  example  given,  100  grams  of  cottonseed  oil  are  mixed  with  1  to 
5  grams  of  nickel  formate  (in  concentrated  aqueous  solution  or  in  the  form  of  a 
powder).  The  mixture  is  warmed  and  a  stream  of  hydrogen  gas  passed  into  the 
apparatus.  During  this  time  the  temperature  of  the  mass  is  raised  to  from  170°  to 
200°  C.  The  duration  of  the  treatment  depends  upon  the  quantity  of  the  catalytic 
agent  employed.  The  reduction  may  be  carried  out  until  the  unsaturated  compounds 
are  quantitatively  transformed  into  saturated  ones.  The  mass  is  then  filtered. 

For  this  process  they  regard  the  metal  salts,  both  normal  and  acid,  of  the  mono- 
and  polybasic  carboxylic  acids  and  hydrocarboxylic  acids  of  the  fatty  groups  as 
most  suitable;  the  formates,  acetates,  propionates,  butyrates,  lactates,  gly collates, 
oxalates,  malonates,  succinates,  tartrates  and  citrates  of  nickel,  cobalt,  iron  and 
copper  are  mentioned. 

"The  process  may  be  modified  in  various  ways.  Thus,  for  example,  the  oil  may 
be  emulsified  with  the  catalytic  agent  and  simultaneously  heated  and  have  hydro- 
gen or  gas  mixtures  containing  hydrogen  passed  through  it  in  a  suitable  emulsifying 
apparatus;  or  the  oil  mixed  with  the  catalytic  agent  may  be  brought  into  contact 
in  a  fine  state  of  division  with  the  hydrogen,  as  in  a  manner  that  has  already  been 
proposed.  The  reaction  may  also  be  accelerated  by  using  the  hydrogen  under 
pressure  or  by  impregnating  the  oil  with  hydrogen  and  then  bringing  it  into  intimate 
contact  with  the  catalytic  agent." 


Fig.  39  is  a  view  of  an  apparatus  for  carrying  out  the  process.  The  gas  is  drawn 
by  a  pump  a  from  a  generator  (not  shown)  and  is  forced  by  the  pump  into  the  pres- 
sure equalizer  6.  Thence  the  gas  passes  through  a  pipe  c,  into  the  receptacle  e  pro- 
vided with  a  funnel  /  for  introducing  the  mixture  of  catalyzer  and  oil.  The  mixing 
apparatus  contains  an  agitator  consisting  of  a  longitudinal  shaft  provided  with  a 
series  of  revolving  beaters  g.  In  the  base  of  the  mixing  apparatus  is  mounted  a 
heater  h.  If  water  gas  is  used  as  the  reducing  agent,  the  portion  of  the  gas,  which 
has  not  been  absorbed  in  the  mixing  apparatus,  passes  through  a  pipe  i  to  a  gas  holder 
or  collector  k,  and  is  then  used  for  heating  or  power  purposes. 

A  modified  form  of  the  inductor  and  tank  shown  in  Fig.  26  is  de- 
picted in  Fig.  40.* 

In  Fig.  40,  1  is  a  treating  receptacle  having  the  inlet  2  for  oil  or  catalyzer;  a 
hydrogen  inlet  3;  a  back-flash  tube  4;  a  draw-off  valve  5;  a  steam  heating  coil  6; 
supporting  members  7;  and  a  catalyzer  inlet  8  adapted  to  hold  capsules  of  catalyzer; 

*  EUis,  U.  S.  Patent  1,084,203,  Jan.  13,  1914. 


METHODS  OF  HYDROGENATION 


49 


11  is  a  pump  connected  with  the  lower  part  of  the  tank  by  the  pipe  12  and  having 
a  discharge  pipe  13  extending  to  an  inductor  14  which  is  in  communication  by  means 
of  the  inlet  15  and  pipe  16  with  the  top  of  the  treating  receptacle  1.  From  the 
inductor  the  pipe  17  extends  nearly  to  the  bottom  of  the  receptacle  and  terminates 
in  a  distributer  18  which  is  so  arranged  that  the  flow  of  material  therethrough  is 
both  down  and  angularly  against  the  bottom  of  the  tank  or  receptacle. 


FIG.  40. 

Bock*  describes  several  forms  of  apparatus  intended  for  hardening 
fats  and  fatty  acids.  One  of  these  involves  passing  the  fatty  material 
along  or  through  a  porous  plate  containing  catalyzer  in  the  presence  of 
hydrogen.  Fatty  acids  may  be  hardened  under  a  considerable  degree 
of  hydrogen  pressure  and  subsequently  the  catalyzer  may  be  freed  from 
the  acid  by  distillation  under  reduced  atmospheric  pressure.  Reduced 
nickel  on  kieselguhr  is  used  as  a  catalyzer,  f 

*  Seifen.  Ztg.,  1914,  349. 

t  See  also  Seifen.  Ztg.,  1914,  421. 


CHAPTER  III 

CATALYZERS  AND  THEIR  ROLE  IN  HYDROGENATION 

PROCESSES 

THE  BASE  METALS  AS  CATALYZERS 

Catalyzers,  those  bodies  which  modify  reaction  velocity  without 
stoichiometrical  participation  in  the  reaction,  are  destined  to  find 
another  important  industrial  application  in  the  hardening  of  oils.* 

For  present  purposes  a  catalyzer  may  be  simply,  though  less  ac- 
curately, defined  as  a  material  or  "  exciter  "  which  brings  about  a 
reaction  between  substances  otherwise  incapable  of  reacting,  the  cata- 
lyzer itself  at  the  end  of  the  reaction  being  unchanged.  Thus  fatty 
oil  and  hydrogen  do  not  unite  readily  unless  nickel  or  some  other 
catalytic  body  is  present  to  serve  as  a  carrier  or  go-between  to  bring 
about  the  reaction. 

The  previous  illustrations  show  the  variety  of  methods  proposed 
for  mingling  oil,  hydrogen  and  catalyzer.  Among  these  are  several 
of  excellent  efficiency.  But,  after  all,  the  virility,  so  to  speak,  of  the 
process,  depends  on  the  catalyzer.  With  a  powerful  catalyzer  the 
hydrogenation  of  oils  becomes  a  rapid,  simple  procedure;  almost,  it 
sometimes  seems,  independent  of  the  nature  of  the  hydrogenating 
apparatus. 

Catalyzers  recognized  as  useful  for  the  purpose  are  nickel  and  palla- 
dium, although  platinum,  copper,  iron  and  other  metals  have  been 
used  to  some  extent.  Nickel  oxide,  as  stated,  has  been  employed  by 
Bedford  and  Ipatiew.  Wimmer  recommends  organic  salts  of  nickel, 
such  as  the  formate,  acetate  or  lactate. 

As  nickel  is  probably  the  most  important  of  these  catalyzers,  in 
view  of  its  efficiency  and  relatively  low  cost,  it  will  be  first  considered.! 

*  Abel.  Zeitsch.  f.  Elektrochem.  (1913),  933-951,  gives  a  bibliography  on  catal- 
ysis. Conroy,  J.  S.  C.  I.,  1902,  302,  discusses  the  industrial  side  of  catalysis.  See 
also  Jobling,  Chem.  World  (1914),  17;  Agulhon,  J.  Agr.  tropicale  (1913),  375;  Stern 
on  Catalysis,  Fortschritte  d.  Chem.  Phys.  u.  Phys.  Chem.  (1913),  249.  A  very  good 
review  of  the  subject  of  oil  hardening  and  the  catalyzers  employed  for  the  purpose 
is  Contributed  by  Meyerheim,  Fortschritte  d.  Chem.  Phys.  u.  Phys.  Chem.  (1913), 
293.  Another  review  appears  in  the  Bulletin  of  the  Imperial  Institute  (1913),  660. 

t  Nickel  is  recommended  as  the  best  catalyzer  for  hardening  whale  oil,  Seifen. 
Ztg.  (1913),  1412. 

50 


CATALYZERS  51 

The  preparation  of  an  effective  nickel  catalyzer  requires  considerable 
care.  The  oxide  or  hydrate  of  nickel  is  first  obtained  by  ignition  of 
nickel  nitrate,  or  precipitation  of  nickel  hydrate  from,  say,  a  nickel 
sulfate  solution  by  the  addition  of  an  alkali.  Obtained  in  this  or  in 
any  other  suitable  manner,  the  next  step  is  the  reduction  to  metallic 
nickel.  For  this  purpose  the  nickel  is  placed  in  a  receptacle  which 
may  be  heated  controllably,  and  hydrogen  gas  is  passed  over  the  mass 
at  a  temperature  ranging  from  250°  to  500°  C.  or  so,  until  water  is  no 
longer  evolved. 

The  most  sensitive  catalyzers  are  obtained  by  reduction  at  the 
lowest  possible  temperatures.  Nickel  begins  to  reduce  below  220°  C., 
but  at  270°  C.  the  reduction  is  not  complete  even  after  long  duration 
of  exposure  to  hydrogen.  A  temperature  of  300°  to  350°  C.  gives 
fairly  complete  reduction  and  is  a  satisfactory  working  range.  The 
lower  the  temperature  at  which  the  nickel  is  reduced,  the  more  sen- 
sitive it  is  to  various  external  influences,  hence  the  preparation  of 
this  catalyzer  should  be  conducted  not  only  with  respect  to  degree  of 
activity,  but  also  with  respect  to  longevity. 

Nickel  is  easily  poisoned  by  chlorine  and  by  sulfur  in  the  sulfide 
form.*  The  author  has  not  experienced  unfavorable  results  from  the 
use  of  hydrogen  gas  passed  through  a  wash  bottle  containing  concen- 
trated sulfuric  acid  and  then  conveyed  directly  to  the  catalyzer  and 
oil.  Traces  of  the  acid  were  entrained  by  the  gas,  but  the  catalyzer 
remained  in  active  condition  during  about  two  weeks  usage  under 
these  conditions. 

Copper  is  much  less  sensitive  to  poisons  than  nickel,  but  on  the 
other  hand  it  is  much  less  active. f 

Catalyzer  made  from  the  heavier  forms  of  the  oxide  without  sup- 
porting material,  weight  for  weight,  is  hardly  as  efficient  as  when  the 
active  surface  is  increased  by  the  use  of  a  carrier.  Hence  we  find 
many  proposals  for  the  production  of  catalyzers  with  a  great  diversity 
of  carriers  and  extenders,  ranging  from  pumice  stone  and  kieselguhr 
to  charcoal  and  sawdust. 

*  The  albumin  contained  in  animal  and  vegetable  fats  and  oils  is  a  source  of 
sulfur-containing  gases  (Bedford  and  Erdmann,  Jour.  f.  prakt.  Chem.,  1913,  426). 

t  Mailhe  (Rev.  gen.  sci.,  24,  650)  describes  the  scientific  and  technical  uses  of 
active  nickel  as  catalyst  in  the  reduction  of  organic  compounds  and  in  the  hydro- 
genation  of  oils.  He  also  discusses  the  catalytic  properties  of  finely-divided  copper 
and  the  commercial  possibilities  of  metallic  oxides  (especially  ThO2)  as  catalytic 
agents  in  processes  requiring  elimination  of  water  (or  water  and  hydrogen,  depending 
on  temperature)  from  organic  compounds.  Drawings  are  given,  showing  forms  of 
apparatus.  Much  stress  is  laid  on  the  maintenance  of  proper  temperatures  and  on 
the  use  of  pure  hydrogen. 


52  THE  HYDROGENATION  OF  OILS 

After  reduction  of  nickel,  as  above,  it  should  be  kept  out  of  contact 
with  air  as  it  is  usually  extremely  pyrophoric  and  quickly  loses  much 
of  its  efficiency  on  exposure  to  the  air.*  Consequently  when  treating 
oil  with  such  a  catalyzer,  it  is  advisable  to  free  the  treating  apparatus 
from  air  by  flushing  with  hydrogen;  also  it  is  sometimes  beneficial  to 
heat  the  oil  and  bubble  hydrogen  through  it  for  a  short  time  prior  to 
the  introduction  of  the  catalyzer. 

The  use  of  nickel  as  a  contact  body  by  Mond,t  in  1888,  is  of  historical 
interest  in  view  of  present  developments.  Mond  found  that  if  car- 
bonic oxide  or  gaseous  hydrocarbons  be  brought  into  contact  with 
metallic  nickel  at  a  temperature  of  350°  to  400°  C.,  or  with  metallic 
cobalt  at  400°  to  450°  C.,  decomposition  takes  place  into  carbon  and 
carbonic  acid  or  hydrogen,  the  carbon  combining  with  the  metal.  If 
now  steam,  at  a  moderate  temperature,  be  introduced,  this  carbon 
combines  with  oxygen  to  produce  carbonic  acid,  with  simultaneous 
formation  of  free  hydrogen.  These  various  reactions  take  place 
simultaneously  when  the  steam  is  passed  through  the  apparatus  along 
with  the  carbonic  oxide  or  hydrocarbon,  the  ultimate  products  being 
carbonic  acid  and  hydrogen.  The  former  can  be  eliminated  by  any 
suitable  means,  such  as  by  washing  with  milk  of  lime.  The  cobalt 
or  nickel  surfaces  may  be  obtained  by  impregnating  pumice  stone  with 
a  solution  of  the  metal,  and  reducing. t 

The  Mond  and  Langer  British  Patent  12,608,  of  1888,  is  entitled  Improvements  in 
Obtaining  Hydrogen.  From  the  specification  the  following  is  quoted: 

"By  the  distillation  or  incomplete  combustion  in  the  presence  or  in  the  absence 
of  steam,  oil,  lignite,  wood,  coke,  animal  carbon  or  organic  substances  in  general, 
gases  are  obtained  which  consist  chiefly  of  hydrogen,  carburets  of  hydrogen,  mon- 
oxide and  dioxide  of  carbon  and  a  greater  or  less  quantity  of  nitrogen.  The  object 
of  our  invention  is  to  eliminate  from  these  gases  the  monoxide  of  carbon  and  the 
carburets  of  hydrogen,  and  at  the  same  time  to  increase  the  amount  of  hydrogen 
contained. 

"  If  a  mixture  of  monoxide  of  carbon  or  carburet  of  hydrogen  and  steam  be  heated 
to  white  heat  in  the  presence  of  firebricks  or  of  oxide  of  iron,  the  latter  is  decomposed 
and  the  carbon  of  the  gases  is  oxidized  to  carbon  dioxide  and  the  hydrogen  set  at 
liberty.  The  high  temperature  required  for  this  reaction  renders  it  of  b'ttle  profit 
and  it  is  difficult  to  produce  it  on  an  industrial  scale.  We  have  found  that  if  mon- 
oxide of  carbon  and  hydrocarburets  be  placed  in  contact  with  metallic  nickel  or 

*  Wimmer  and  Higgins  (Seifen.  Ztg.  (1913),  556)  prepare  catalyzer  by  reducing 
the  active  material  while  it  is  enveloped  in  a  protecting  material,  oil  being  recom- 
mended for  this  purpose. 

t  British  Patent  12,608,  Sept.  1,  1888. 

t  The  use  of  nickel  in  the  catalytic  reduction  of  carbon  monoxide  to  methane  is 
set  forth  in  U.  S.  Patents  to  Elworthy  738,303,  Sept.  8,  1903;  777,848,  Dec.  20, 
1904;  and  943,627,  Dec.  14,  1909. 


CATALYZERS  53 

cobalt  at  a  temperature  not  exceeding  a  red  heat,  these  gases  are  decomposed  into 
carbon  and  dioxide  of  carbon  on  the  one  hand  and  hydrogen  on  the  other;  the  free 
carbon  so  formed  placed  in  contact  with  steam  at  a  moderate  temperature  decom- 
poses the  latter  and  forms  dioxide  of  carbon  and  hydrogen. 

"  If  the  steam  and  the  gases  are  mixed  from  the  commencement,  the  two  reactions 
take  place  simultaneously  and  the  result  is  a  gas  practically  free  from  monoxide  of 
carbon  and  hydrocarburets.  It  is  quite  possible  to  attain  our  object  by  carrying 
out  consecutively  the  two  above-mentioned  reactions  and  by  repeating  them  con- 
tinually with  the  same  quantity  of  nickel  and  cobalt  which  will  always  be  regen- 
erated. We  prefer,  however,  to  carry  out  these  two  reactions  simultaneously, 
at  the  same  time  employing  the  least  possible  amount  of  nickel  and  cobalt;  with 
this  object  we  spread  the  aforesaid  metals  on  an  indifferent  refractory  and  porous 
material.  For  example,  we  saturate  pieces  of  pumice  stone  with  a  solution  of  chloride 
of  nickel  or  cobalt,  dry  and  reduce  at  a  higher  temperature  with  hydrogen, 

"In  carrying  out  our  invention  industrially  we  lead  the  gases  with  an  excess  of 
steam  into  retorts  or  cylinders  fixed  in  a  suitable  furnace  and  containing  pieces  of 
pumice  stone  impregnated  with  nickel  or  cobalt  as  above  mentioned.  When  nickel 
is  used,  the  reaction  takes  place  at  a  temperature  of  350°  to  400°  C.  If  cobalt  be 
used,  at  a  temperature  of  400°  to  450°  C.  The  reactions  which  take  place  between 
the  gas  and  the  steam  produce  heat  so  that  the  given  temperature  once  reached  the 
reaction  goes  on  of  itself  without  need  of  external  heating. 

"  It  may,  however;  be  advantageous  to  use  gases  or  steam  or  both,  heated  to  a 
suitable  temperature  before  they  are  placed  in  the  retorts.  The  gases  so  treated 
contain  little  or  no  monoxide  of  carbon.  The  carbonic  acid  can  be  separated  in  any 
known  manner,  such  as  by  passing  the  gases  through  lime  or  caustic  alkali. 

"  The  foregoing  process  differs  entirely  from  the  plan  of  using  an  easily  reduced 
oxide  and  oxidizing  the  carbonic  oxide  or  hydrocarbons  by  means  of  that  oxide  at 
a  bright  red  heat,  as  in  our  case  no  oxide  is  used,  but  a  metal  having  but  little  affin- 
ity for  oxygen,  but  a  considerable  affinity  for  carbon.  The  metal  deprives  the 
carbonic  oxide  of  a  part  of  its  carbon  and  gives  the  latter  up  to  the  oxygen  of  the 
steam.  This  is  done  at  a  heat  much  below  that  at  which  oxide  of  iron  or  other  like 
oxide  would  give  up  its  oxygen." 

Mond  and  Langer  lay  claim  to  the  process  of  obtaining  hydrogen  by  means  of 
gases  containing  carbon  monoxide  with  or  without  hydrocarbons  which  consists  in 
treating  such  gases  with  metallic  nickel  or  cobalt  and  with  steam  and  separating 
from  the  hydrogen  the  carbonic  acid  resulting  from  such  a  treatment. 

They  also  claim  the  use  of  pumice  stone  or  other  similar  porous  substance  impreg- 
nated with  one  or  more  salts  of  cobalt  or  nickel  so  as  to  provide,  when  reduced,  an 
extended  metallic  surface  with  only  a  small  amount  of  actual  metal. 

These  extracts  are  given  because  of  the  use  by  Mond  and  Langer,  in  1888,  of 
reduced  nickel  or  cobalt  on  porous  refractory  material  for  catalytic  purposes,  although, 
to  be  sure,  the  object  of  the  process  was  to  produce  hydrogen  rather  than  to  cause 
its  combination  with  unsaturated  bodies. 

Carbon  and  hydrogen  combine  with  difficulty,  especially  to  form  methane.  At 
the  ordinary  pressure  in  the  presence  of  nickel  oxide,  reduced  nickel  or  a  mixture 
of  nickel  and  alumina,  and  up  to  625°  C.,  there  is  no  formation  of  methane.  Under 
great  pressures  its  synthesis  only  occurs  above  500°  C.  in  the  presence  of  the  above 
substances  or  mixtures,  and  so  much  the  better  as  the  temperature  becomes  greater. 
In  the  presence  of  water  and  nickel,  methane  is  decomposed  at  500°  C.  into  hydrogen 
and  carbonic  acid.  The  inverse  reaction,  i.e.,  reduction  of  carbonic  acid  to  methane 


54  THE  HYDROGENATION  OF  OILS 

in  the  presence  of  nickel  and  an  excess  of  hydrogen  at  ordinary  pressure,  occurs  at 
450°  C.  Results  are  the  same  with  nickel  oxide.  (Chem.  Trade  Jour.,  Oct.  25,  1913, 
414.) 

At  ordinary  pressure  no  methane  is  formed  by  combination  of  its  elements  in 
the  presence  of  catalyzers  such  as  nickel  or  nickel  oxide,  but  under  high  pressures 
and  at  a  temperature  of  510°  to  520°  C.,  methane  is  formed.  (Ipatiew  Chem.  Ztg. 
Rep.  (1914),  15.) 

Acetylene  is  converted  into  ethylene  by  treatment  with  hydrogen  under  pres- 
sure in  the  presence  of  catalyzers.  The  Elektro  Chemische  Werke  G.  m.  b.  H. 
(Zeitsch.  f.  angew.  Chem.  (1913),  ref.  644)  find  that  the  production  of  ethylene  from 
acetylene  and  hydrogen  on  a  commercial  scale  is  difficult,  due  to  the  gradual  loss 
in  the  efficiency  of  the  catalyzer.  Even  though  the  usual  precautions  are  taken  to 
remove  the  recognized  poisons,  such  as  hydrogen  sulfide,  sulfurous  acid,  chlorine 
and  the  like,  there  still  remain  in  the  gas  certain  impurities  which  cannot  be  elimi- 
nated by  the  usual  absorption  reagents.  Accordingly  it  is  recommended  to  wash 
the  hydrogen  with  concentrated  sulfuric  acid,  then  to  pass  it  over  solid  caustic 
soda,  which  treatment  is  said  to  remove  the  troublesome  bodies.  To  effect  the 
combination  of  the  unaltered  ethylene  and  hydrogen  in  the  gaseous  mixture  resulting 
from  the  passage  of  these  gases  over  a  catalyst,  the  product  is  again  passed  over 
the  catalyst  under  pressure.  The  reaction  is  stated  to  be  quantitative  and  instan- 
taneous. Nickel  or  a  metal  of  the  platinum  group  may  be  used  as  a  catalyst. 
(German  Patent  265,171,  Oct.  16,  1912.) 

From  a  very  lengthy  paper  published  by  Sabatier  and  Senderens  * 
the  following  items  on  the  preparation  and  use  of  catalyzers  have  been 
noted. 

Access  of  air  to  the  catalyzer  oxidizes  it  and  destroys  or  diminishes 
its  activity.  To  prepare  catalytic  material  one  should  use  an  oxide 
quite  free  of  chlorine  or  sulfur.  Good  results  are  obtained  by  dis- 
solving the  metal  in  pure  nitric  acid  and  forming  the  oxide  by  calcina- 
tion at  a  low  red  heat.  Reduction  of  the  oxide  should  be  with  pure 
hydrogen,  free  from  chlorine  or  sulfur.  Reduction  should  take  place 
at  a  low  temperature,  always  below  a  red  heat,  or  the  catalyzer  will  not 
be  efficient. 

Nickel  reduced  at  a  red  heat  has  practically  no  activity.  At  300°  C. 
it  gives  a  very  active  material  if  used  immediately.  It  is  better,  how- 
ever, to  employ  a  temperature  of  350°  C.  Copper  is  best  treated  at 
300°  C.,  while  cobalt  f  requires  400°  C.  Iron  is  difficult  to  reduce. 
At  450°  C.  some  6  or  7  hours  are  required  to  completely  transform  the 
oxide  into  the  metal.  Nickel  and  copper  are  actually  reduced  near 
200°  C.,  so  even  if  some  oxidation  of  the  catalyzer  were  taking  place, 

*  Ann.  de  China,  et  de  Phys.,  1905  (4),  319. 

t  The  reduction  of  cobalt  oxides  by  hydrogen  and  carbon  monoxide  at  different 
temperatures  is  described  by  Kalmus.  (Jour.  Ind.  Eng.  Chem.  (1914),  112-114.) 
For  some  metals  the  minimum  temperature  of  reduction  is  lower  with  carbon  mon- 
oxide than  with  hydrogen  (Fay  and  Seeker,  J.  Am.  Chem.  Soc.,  1903,  641). 


CATALYZERS 

because  of  the  presence  of  oxygen  in  the  hydrogen  gas,  immediate 
reduction  would  occur  thereafter. 

The  hydrogen  employed  is  dried  with  sulfuric  acid,  is  then  passed 
through  a  tube  of  Jena  glass  filled  with  copper  turnings  maintained 
at  a  low  red  heat  and  finally  goes  through  a  long  tube  filled  with 
fragments  of  caustic  potash. 

The  catalyzer  should  be  prepared  in  the  tube  in  which  the  material 
to  be  hydrpgenated  is  treated. 

For  high  temperatures  a  copper  tube  heated  in  a  bath  of  equal  parts 
of  sodium  and  potassium  nitrate  (which  melts  at  225°  C.)  may  be 
used. 

With  regard  to  the  life  of  the  catalytic  material  the  investigators 
state  that  there  are  three  periods  noticeable. 

1.  A  short  period  when  the  catalyzer  is  becoming  accustomed  to 
the  atmosphere  of  hydrogen  and  the  body  to  be  treated. 

2.  A  period  of  normal  activity. 

3.  A  period  of  decline.* 

The  second  or  normal  period  is  generally  very  long,  if  no  trace  of 
bodies  capable  of  altering  the  surface  of  the  metal  is  present.  For 
example,  with  a  nickel  catalyzer  good  results  were  secured  for  one 
month  in  the  transformation  of  benzene  into  cyclohexane.  The 
operation  was  interrupted  each  night  and  resumed  the  next  morning. 
The  slight  oxidation  over  night  did  no  harm  as  the  oxide  was  reduced 
again  the  next  day  at  the  temperature  of  working,  which  was  180°  C. 

If  in  the  hydrogen  there  is  a  trace  of  certain  bodies,  the  action  of  the 
catalyzer  is  rapidly  suppressed.  Even  tiny  traces  of  chlorine,  bromine, 
iodine  or  sulfur  paralyze  the  nickel.  Nickel  obtained  from  oxide 
carrying  a  little  chlorine  is  usually  devoid  of  activity.  Nickel  from 
oxide  containing  a  trace  of  sulfur  is  likewise  inefficient.  The  pres- 
ence in  the  hydrogen  of  even  faint  traces  of  hydrochloric  acid,  hydro- 
gen sulfide  or  selenium  compounds  produces  the  same  disastrous 
effects.  Traces  of  bromine  in  some  phenol  which  was  used  paralyzed 
the  nickel.  The  same  thing  happened  with  benzol  containing  this 
compound. 

Catalyzers  finally  lose  their  efficiency  either  by  traces  of  poisons 
or  by  a  deposit  of  tarry  or  carbonaceous  material  on  the  catalyzer 
particles.  On  dissolving  spent  nickel  in  hydrochloric  acid  a  fetid 
gas  is  evolved  and  brown  carbonaceous  material  is  deposited. 

According  to  Sabatier  and  Senderens  the  operation  should  be  con- 
ducted to  prevent  liquid  coming  into  contact  with  catalyzer.  The 
temperature  limits  practically  are  those  imposed  by  maintaining  the 
*  These  periods  are  similar  to  those  noted  in  the  case  of  ferments. 


56  THE  HYDROGENATION  OF  OILS 

substance  in  a  state  of  vapor.  Too  high  temperatures  sometimes 
cause  decomposition.  Benzene  becomes  cyclohexane  at  tempera- 
tures up  to  240°  C.,  but  at  300°  C.  the  cyclohexane  gives  benzene  and 
methane : 

3  C6H12  =  2  C6H6  +  6  CH4. 

Copper  and  platinum  work  well  in  case  of  ethylene  groups,  but  are 
not  satisfactory  for  hydrogenation  of  the  aromatic  ring.  Nickel  is 
effective  on  the  latter.* 

Some  peculiarities  of  catalytic  nickel  have  been  recorded  by  Sen- 
derens  and  Aboulenc.f  These  investigators  state  that  the  tempera- 
ture at  which  nickel  oxide  is  reduced  by  hydrogen  is  found  to  depend 
on  the  mode  of  preparation  and  treatment  of  the  oxide  used,  there 
being  also  a  considerable  difference  between  the  temperature  at  which 
reduction  commences  and  that  at  which  it  is  complete.  Complete 
reduction  is  not  effected  below  300°  C.,  but  the  mixture  of  metal  and 
oxide  thus  obtained  is  more  active  than  the  metal  prepared  by  total 
reduction  at  a  higher  temperature,  the  activity  of  reduced  nickel  being 
diminished  by  heating  to  a  comparatively  high  temperature,  although, 
at  the  same  time,  its  catalytic  properties  are  rendered  more  permanent. 
Pyrophoric  nickel,  when  heated  in  the  air,  furnishes  an  oxide  which 
is  reducible  at  a  comparatively  low  temperature,  and  reduced  nickel 
of  impaired  activity  may  be  restored,  therefore,  by  oxidizing  it  and 
again  reducing. 

According  to  Moissan  the  protoxide  of  nickel  in  hydrogen  at  230°  to 
240°  C.  blackens  and  reduces,  giving  a  body  pyrophoric  at  ordinary 
temperature.  Muller  states  the  protoxide  of  nickel  at  210°  to  214°  C. 
in  hydrogen  loses  11  to  14  per  cent  of  oxygen,  apparently  giving 
nickelous  oxide  which  corresponds  to  a  loss  of  10.7  per  cent  oxygen. 
At  270°  C.  it  passes  into  the  metallic  state.  For  hydrogenation  the 
anhydrous  or  hydrated  oxide  of  nickel  supported  on  pumice  is  reduced 
at  270  to  280  degrees  (Brunei) ;  280  degrees  (Leroux) ;  255  to  260  de- 
grees (Godchot) ;  245  to  250  degrees  (Darzens) . 

Senderens  and  Aboulenc,  however,  after  a  protracted  investigation, 
recorded  results  which  in  brief  are  as  follows: 

(a)  Anhydrous  nickel  oxide:  This  oxide  becomes  green  a  little 
above  200°  C.  in  presence  of  hydrogen,  but  the  reduction  commences 
only  at  about  300°  C.  and  is  slow  at  330°  C.  It  goes  on  much  faster 

*  Sabatier  has  reviewed  the  subject  of  catalytic  action  in  organic  chemistry,  the 
publication  appearing  as  Vol.  Ill  of  the  Encycl.  de  Science  Chimique  applique  aux 
arts  industriels. 

t  Bull.  Soc.  Chim.  (1912),  n,  641. 


CATALYZERS  57 

at  380°  C.  up  to  two-thirds  the  amount  of  water  which  should  be 
evolved.  There  reduction  stops.  To  get  complete  reduction  the 
temperature  has  to  be  raised  to  420°  C.  The  nickel  obtained  is 
pyrophoric.  It  serves  very  well  for  the  hydrogenation  of  carbon 
monoxide,  carbon  dioxide,  benzene  and  toluene,  but  does  not  work 
well  with  the  phenols. 

(&)  Nickel  oxide  obtained  by  calcination:  This  shows  a  great  re- 
sistance to  reduction.  It  is  necessary  to  raise  the  temperature  to 
420°  C.  to  obtain  two-thirds  of  the  water  of  theory  and  to  a  red  heat 
to  secure  complete  reduction.  Heated  to  this  last-named  temperature 
the  product  is  inactive  even  with  carbon  monoxide  which  is  very  easily 
hydrogenated.  It  is  pyrophoric,  however.  The  efficiency  of  nickel 
as  a  catalyzer  does  not  depend  on  any  pyrophoric  property.  Non- 
pyrophoric  nickel  has  been  prepared  which  is  a  good  catalyzer.  Re- 
duction of  the  oxide  (6)  at  420°  C.  gives  about  one-third  oxide  with 
two-thirds  metal.  This  mixture  is  active  and  pyrophoric.  It  easily 
converts  water  gas  into  methane. 

(c)  Hydrate  of  nickel :  Introducing  hydrate,  prepared  in  the  labora- 
tory, into  the  tube  used  for  reduction,  the  dehydration  was  very  slight 
at  200°  C.,  while  at  230°  C.  reduction  took  place  and  at  270°  C.  de- 
hydration and  reduction  progressed,  but  rather  slowly.  In  another 
experiment  the  same  "  hydrate  "  was  reduced  after  gently  heating  in 
a  crucible  to  remove  the  water.  The  reduction  presented  the  same 
variations  commencing  about  230°  C.  and  progressing  very  gently 
up  to  270°  C.  at  which  point  water  was  given  off  regularly  for  6  hours 
in  an  amount  corresponding  to  one-third  the  total  expected  from  the 
reduction  of  the  oxide.  At  300°  C.  two- thirds  of  the  water  was  col- 
lected and  at  320°  C.  the  remainder  was  obtained  after  treatment  for 
several  hours. 

Another  hydrate  of  nickel  furnished  by  a  chemical  supply  house 
was  more  difficult  to  reduce,  not  giving  off  as  much  water  as  the  pre- 
ceding at  temperatures  20  to  30  degrees  higher. 

Oxides  of  pyrophoric  nickel:  These  may  be  obtained  by  letting 
pyrophoric  nickel  oxidize  in  a  thin  layer  in  the  cold  or  by  heating.  In 
the  cold  the  oxidation  is  variable;  when  heated  the  reaction  is  com- 
plete in  a  moment.  The  oxides  obtained  in  this  manner  commence 
to  reduce  at  a  temperature  much  lower  than  those  from  which  the 
pyrophoric  nickel  was  derived.  For  example,  the  oxide  resulting 
from  the  simple  exposure  to  the  air  of  the  pyrophoric  nickel  obtained 
from  the  hydrate  (c)  was  reduced  at  210°  C.  by  hydrogen,  giving  about 
one-half  the  theoretic  water. 

The  oxide  obtained  by  moderate  calcination  in  the  air  of  this  same 


58  THE  HYDROGENATION  OF  OILS 

pyrophoric  nickel  takes  up  hydrogen  at  250°  C.  giving  off  half  the 
theoretic  water;  after  which,  to  complete  the  reduction  it  is  neces- 
sary to  raise  the  temperature  as  in  the  preceding  case. 

The  anhydrous  oxide  (a)  commenced  to  reduce  at  300°  C.,  reduction 
was  slow  at  330°  C.  and  normal  only  at  380°  to  420°  C.  The  pyro- 
phoric metal  which  results  when  this  material  is  heated  in  contact  with 
air  furnishes  an  oxide  of  which  one-third  is  reduced  at  280°  C.  and 
half  at  320°  C.  The  activity  of  the  nickel  reduced  from  these  oxides 
is  at  least  equal  if  not  superior  to  that  obtained  by  the  reduction 
of  the  normal  oxide. 

When  the  nickel  begins  to  weaken  in  catalytic  effect  it  is  necessary 
only  to  oxidize  and  then  reduce  it,  in  order  to  have  the  catalyzer  com- 
pletely regenerated. 

Passivity  of  nickel  as  a  catalyzer:  If  used  to  hydrogenate  phenol 
for  a  day  or  two  it  will  then  hydrogenate  cresol,  but  if  used  for  a  month 
on  phenol  it  will  not  be  active  on  cresol,  although  still  active  on  phenol. 
By  oxidizing  and  then  reducing,  the  material  is  very  active  on  cresol. 

Anhydrous  oxides  and  hydrates  of  nickel  cannot  be  completely 
reduced  to  the  metal  at  300°  C.,  but  a  mixture  of  the  metal  and  oxide 
results.  It  is  nevertheless  true  that  such  mixtures  are  more  active 
than  if  complete  reduction  with  corresponding  elevation  of  the  tem- 
perature had  taken  place. 

Two  stages  of  oxidation,  derived  from  the  same  pyrophoric  nickel  of 
which  in  one  case  the  reduction  was  arrested  at  250°  C.  when  one-half 
the  oxide  remained,  and  in  the  other  case  the  material  was  heated 
up  progressively  to  350°  C.  to  give  total  reduction,  were  tested.  The 
latter  hydrogenated  xylenol  normally,  while  the  former  gave  a  hydro- 
carbon. To  evade  this  destructive  action  in  a  number  of  cases  the 
investigators  heated  the  nickel  after  reduction  to  a  higher  temperature 
to  diminish  its  activity  and  conserve  its  life  as  a  catalyzer.* 

*  Padoa  and  Fabris  (J.  S.  C.  I.,  1908,  1083)  showed  that  at  ordinary  pressure 
indene  is  not  capable  of  combining  with  hydrogen  in  presence  of  reduced  nickel 
at  300°  C.,  but  that  at  250°  C.  two  atoms  of  hydrogen  are  taken  up.  Ipatiew 
(J.  Russ,  Phys.  Chem.  Soc.  (1913),  45,  994)  finds  that  in  presence  of  nickel  oxide, 
indene  unites  with  hydrogen  at  250°  to  260°  C.  and  110  atmospheres,  yielding  the 
hydrocarbon  octohydroindene.  The  nature  of  the  metal  of  which  Ipatiew's  high- 
pressure  apparatus  (J.  S.  C.  I.,  1911,  239)  is  constructed  is  found  to  exert  an  influ- 
ence on  the  hydrogenation,  in  presence  of  cuprous  oxide,  of  compounds  containing 
ethylene  linkages.  Thus,  in  an  iron  tube,  amylene  (trimethylethylene)  is  readily 
converted  into  isopentane,  while  in  a  copper  tube  the  reaction  is  incomplete,  an 
equilibrated  mixture  of  amylene,  hydrogen  and  isopentane  remaining: 

CsHio  -f-  H.2  <=^  CgHi2. 
In  an  iron  tube  and  in  absence  of  cupric  oxide,  no  hydrogenation  occurs.     Similar 


CATALYZERS  59 

Several  types  of  catalyzers  have  been  proposed  for  oil  hardening 
and  in  some  cases  processes  have  been  prescribed  for  operation  with 
specific  catalyzers.  From  the  standpoint  of  the  support  or  carrier  for 
the  primary  active  material  catalyzers  may  be  divided  into  several 
well-defined  groups,  each  exhibiting  characteristic  properties.  The 
classification  embraces : 

CLASSIFICATION  OF  CATALYZERS 

Group  A 
I.   Carrier  porous,  inert  and  coated  but  is  not  impregnated  with 

catalytic  metal. 

II.    Carrier  active,  serving  as  a  secondary  catalyzer  or  feeder,  is 
coated  but  not  impregnated  with  catalytic  metal. 

Group  B 

I.   Carrier  non-porous,  inert  and  is  fairly  evenly  coated  with  cata- 
lytic metal. 

II.   Carrier   non-porous,   inert   and   instead   of   being   coated   is 
punctated  with  metal  nodules. 

III.  Carrier  non-porous,  active  and  is  fairly  evenly  coated  with 

catalytic  metal. 

IV.  Carrier  non-porous,  active,  serving  as  a  secondary  catalyzer 

or  feeder  and  instead  of  being  evenly  coated  is  punctated 
with  metal  nodules. 

Group  C 

I.   Carrier  porous,  inert  and  is  impregnated  with  catalytic  metal. 
II.   Carrier  porous,  active,  serving  as  a  secondary  catalyzer  and 

is  impregnated  with  catalytic  metal. 

Other  subdivisions  follow  if  the  catalytic  material  is  used  in  a 
coarse  condition  or  in  a  finely-divided  state,  etc.  Superficially  treated 
or  coated  carriers  are  regarded  as  more  desirable  for  treating  liquids, 
while  the  porous  impregnated  varieties  find  a  better  field  of  utility  in 
the  hydrogenation  of  gases  or  vapors  which  in  admixture  with  hydrogen 
are  capable  of  penetrating  porous  bodies  into  which  viscous  liquid 
compounds  would  not  readily  diffuse. 

results  are  obtained  with  hydro-aromatic  compounds.  Further,  hydrogenation  in 
an  apparatus  of  phosphor  bronze  in  presence  of  reduced  copper  results  in  the  estab- 
lishment of  an  equilibrium, ,  while,  if  iron  turnings  are  also  present,  hydrogenation 
proceeds  to  an  end.  The  slight  catalytic  activity  of  reduced  copper  in  copper  tubes 
may  be  regarded  as  due  to  poisoning  of  the  catalyst;  or  the  use  of  cupric  oxide  in 
iron  tubes  may  result  in  a  conjugated  catalytic  action. 

Ipatiew  (Chem.  Centralbl.  (1906),  II,  87)  found  alumina  to  act  as  a  dehydro- 
genating  catalyzer  on  various  bodies. 


CHAPTER  IV 
THE  BASE   METALS  AS   CATALYZERS 

NICKEL  CATALYZERS  —  Continued 

Nickel  oxide  catalyzer  is  recommended  by  Bedford  and  Erdmann* 
as  preferable  to  the  metallic  forms  and  some  of  the  features  claimed  for 
this  material  are  noted  in  the  following:  They  indicate  that  the  hy- 
drogenation  of  oils  by  means  of  finely-divided  nickel,  although  now 
worked  on  a  commercial  scale,  has  the  disadvantage  that  the  catalyst 


FIG.  41.  —  Photo-micrograph  of  a  particle  of  crushed  glass  coated  with  nickel  oxide 
(equivalent  to  10  per  cent  of  metallic  nickel). 

is  extremely  sensitive  to  small  quantities  of  air  and  to  traces  of  chlorine 
and  sulfur  compounds,  which  latter  may  be  developed  from  protein, 
always  present  in  vegetable  and  animal  oils.  Oxides  of  nickel  are 
capable  of  acting  as  hydrogen  carriers  for  the  hydrogenation  of  oils  at 
atmospheric  pressure,  and  possess  the  advantage  over  metallic  nickel 
of  being  relatively  insensitive  to  gases  containing  oxygen  and  sulfur 
compounds;  moreover  hydrogenation  proceeds  with  much  greater 
velocity  than  with  metallic  nickel.  Any  one  of  the  oxides  of  nickel 
may  be  used,  viz.,  nickel  sesquioxide,  nickel  monoxide  or  nickel  sub- 

*  J.  Prakt.  Chem.  (1913),  87,  425. 
60 


THE  BASE  METALS  AS  CATALYZERS 


61 


oxide;*  with  the  sesquioxide  and  monoxide  a  temperature  of  about 
250°  C.  is  required,  but  with  nickel  suboxide  180°  to  200°  C.  is  suffi- 
cient. When  the  higher  oxides  of  nickel  are  used  they  become  partially 
reduced  to  the  suboxide  which  is  said  to  form  a  colloidal  suspension  in 
the  oil.  Hence  a  nickel  oxide  catalyst  becomes  more  active  after  it 
has  been  used,  owing  to  the  formation  of  the  suboxide.  No  reduction 
to  metallic  nickel  occurs  during 
the  hydrogenation  process,  al- 
though in  absence  of  oil,  reduc- 
tion of  nickel  oxides  to  metallic 
nickel  by  hydrogen  takes  place 
at  190°  C.  Nickel  suboxide  may 
be  distinguished  from  metallic 
nickel  by  its  lack  of  electric  con- 
ductivity and  by  its  inability 
to  form  nickel  carbonyl  when 
treated  with  carbon  monoxide 
under  pressure  at  a  moderate 
temperature.  Other  metallic  ox- 
ides (e.g.,  copper  oxide,  ferrous 
oxide)  are  also  capable  of  acting 
as  catalyzers  in  the  hydrogen- 
ation of  oils,  but  do  not  act  so 
well  as  nickel  oxide.  The  activ- 
ity of  nickel  oxide  is  increased  by  small  quantities  of  the  oxides  of 
aluminium,  silver,  zirconium,  titanium,  cerium,  lanthanum  and  mag- 
nesium. Nickel  salts  of  organic  acids  do  not  act  as  catalysts, 
but  in  presence  of  the  heated  oil  are  decomposed  by  hydrogen, 
yielding  nickel  oxides  and,  under  certain  conditions,  also  metallic 
nickel;  the  resultant  nickel  material  then  acts  as  a  catalyst.  Nickel 
formate  in  the  presence  of  the  heated  oil  is  reduced  by  hydrogen  to 
nickel  suboxide  at  210°  C.,  while  at  250°  C.  metallic  nickel  is  also 
produced.  In  carrying  out  the  hydrogenation,  the  oil  is  placed  in  a 
cylindrical  copper  vessel  fitted  with  an  agitator,  and  heated  in  an  oil 
bath  to  180°  C.  while  a  slow  current  of  hydrogen  is  passed  through.  A 
small  quantity  of  nickel  oxide  is  then  added,  the  temperature  is  raised 
to  255°  to  260°  C.,  a  further  addition  of  the  catalyst  is  made  and  the 
supply  of  hydrogen  is  increased.  The  hydrogenation  is  controlled  by 
examining  test-samples  of  the  oil  as  to  melting  point  and  iodine  value. 
The  oil  becomes  black  possibly  owing  to  the  formation  of  "  col- 

*  Compare  Moore,  Chem.  News  (1895),  7182.     Bohm  (Seifen.  Ztg.  (1912),  1044) 
briefly  discusses  oxide  catalyzers.     See  also  Soap  Gazette  and  Perfumer,  1913,  107. 


FIG.  42.  —  Photo-micrograph  of  a  particle 
of  crushed  glass  coated  with  10  per  cent 
of  reduced  nickel. 


62  THE  HYDROGENATION  OF  OILS 

loidal "  nickel  suboxide,  which  passes  through  a  filter-paper,  but  can 
be  removed  by  centrifuging.  Nickel  soaps  are  formed  only  to  a  slight 
extent,  and  probably  in  consequence  of  a  secondary  reaction  during 
the  cooling..  The  hydrogenized  fat  is  free  from  hydroxy-acids.  The 
catalyst  after  use  contains  some  organic  matter  apparently  composed 
partly  of  nickel  palmitate  or  stearate,  and  other  substances,  one  of 
which  probably  is  nickel  carbide.  The  process  is  easy  to  control  if 
pure  hydrogen  is  available,  and  in  an  experimental  plant  of  1  ton 
capacity  Bedford  and  Erdmann  report  that  more  than  100  tons  of 
different  oils  have  been  hardened  by  hydrogenation  in  the  manner 
described. 

Nickel  oxide  catalyzers  have  been  made  the  subject  of  a  number  of 
patents. 

English  Patent  4702,  of  1912,  to  Boberg  and  the  Techno-Chemical 
Laboratories,  Ltd.,  London,  proposes  to  prepare  catalyzer  through  the 
reduction  of  a  metallic  compound  such,  for  example,  as  ignited  nickel 
carbonate,  the  reduction  taking  place  with  hydrogen  under  such  con- 
ditions that  the  nickel  contains  one  or  more  suboxides,  or  when  nickel 
is  employed  a  compound  is  formed  which  contains  less  oxygen  than 
the  ordinary  oxide  NiO.* 

The  observation  is  made  that  in  the  reduction  of  ignited  nickel  car- 
bonate by  hydrogen  the  product  obtained  is  just  so  much  more  effi- 
cient catalytically  the  lower  the  temperature  at  which  the  reduction 
takes  place,  because  of  the  suboxide  formed.  The  catalyzer  apparently 
also  contains  some  hydrogen.  The  preparation  of  the  catalyzer  is 
carried  out  by  passing  ignited  nickel  carbonate,  free  from  injurious 
impurities,  continuously  in  a  slow  stream  through  an  inclined  rotary 
cylinder,  which  is  heated  in  part  or  throughout  its  length,  while  hydro- 
gen is  allowed  to  flow  through  in  an  opposite  direction.  By  suitable 
regulation  of  the  influx  of  the  material  as  well  as  the  proper  regulation 
of  the  temperature,  the  reduction  may  be  carried  out  in  such  a  manner 
that  one  obtains  a  catalyzer  which  is  partly  or  mainly  composed  of  the 
suboxide.  The  most  suitable  temperature  is  between  230°  to  270°  C. 
and  the  length  of  the  heating  operation  must  be  just  so  much  more 
prolonged  the  lower  the  maintained  temperature.  Unnecessarily 
long  heating  must  be  avoided  otherwise  the  reduction  goes  too  far 
which  causes  a  diminution  in  catalytic  activity.  The  catalyzer  so 
obtained  can  be  used  immediately  for  oil  hardening  or  it  may  be  pre- 

*  The  proposal  by  Boberg  to  prepare  a  catalyzer  from  nickel  carbonate  by  ignition 
and  reduction  to  form  a  mixture  of  nickel  and  its  suboxide  is  criticized  by  the  editor 
of  the  Chemiker  Zeitung  (Chem.  Ztg.  (1913),  481)  as  offering  nothing  novel  in  view 
of  Bedford's  disclosures  in  English  Patent  29,612,  1910. 


THE  BASE  METALS  AS  CATALYZERS  63 

served  in  contact  with  air  where  it  oxidizes  very  slowly,  provided  local 
over-heating  is  avoided. 

One  can  also  collect  the  catalyzer  in  water,  filter  and  dry  in  the  air; 
or  it  can  be  collected  in  an  atmosphere  of  hydrogen  which  is  gradually 
displaced  by  air. 

The  production  of  suboxide  catalysts  is  also  carried  out  by  reducing 
nickel  oxide  as  completely  as  possible  and  then  controllably  oxidizing 
the  product  in  any  suitable  way  as  with  air  or  oxygen  diluted  with  an 
indifferent  gas,  such  as  carbon  dioxide,  so  that  the  introduction  of 
oxygen  can  progress  without  local  overheating.  Such  oxidation  can 
go  on  between  300°  to  600°  C. 

The  degree  of  catalytic  activity  of  a  metal  oxide  depends  not  only 
on  its  chemical  but  also  on  its  physical  properties.  It  is  known  that 
metal  catalyzers,  such  as  nickel,  cobalt  and  iron,  require  very  fine 
division  for  effective  action.  The  same  is  also  true  of  the  oxides  of 
these  metals.  The  German  Patent  to  Erdmann  and  Bedford  (260,009, 
1911)  relates  to  oxide  catalyzers  in  a  voluminous  form.  The  patentees 
state  that  metal  oxides  may  be  obtained  in  the  form  of  an  especially 
finely-divided  voluminous  material  if  one  takes  a  concentrated  aqueous 
solution  of  the  nitric  acid  salt  from  which  the  oxide  is  to  be  made, 
mixes  with  it  a  water-soluble  organic  compound  rich  in  carbon  and 
then  subjects  the  mixture  to  combustion  by  allowing  it  to  fall,  drop 
by  drop,  into  a  heated  vessel.  The  strong  evolution  of  gas  which  thus 
takes  place,  due  to  the  combustion  of  the  organic  compound  and 
simultaneous  decomposition  of  the  nitrate,  produces  nickel  oxide  in  a 
very  voluminous  form.  Especially  recommended  for  this  purpose  are 
the  sugars  and  carbohydrates,  for  these  when  heated  by  themselves 
produce  a  strongly-swelling  carbonaceous  mass.* 

As  an  example  Erdmann  and  Bedford  state  that  nitric  acid  of  1.42 
specific  gravity  is  diluted  with  an  equal  volume  of  water.  Pure  metal- 
lic nickel  is  introduced.  After  the  reaction  is  complete  the  solution  is 
heated  for  two  hours  with  an  excess  of  nickel  in  order  to  completely 
neutralize  the  nitric  acid  and  to  separate  any  iron  present  as  a  pre- 
cipitate of  iron  hydroxide.  The  clarified  nickel  nitrate  solution  is 
evaporated  to  specific  gravity  of  1.6  and  to  one  liter  of  this  fluid,  cor- 
responding to  250  grams  of  nickel,  180  grams  of  powdered  cane  sugar 
are  introduced.  This  solution  is  allowed  to  run  in  portions  into  a 
muffle  heated  to  a  low  red  heat.  Each  portion  is  heated  until  no 

*  The  use  of  sugar  or  gum  in  a  somewhat  similar  manner  has  been  described  by 
Schroeder  (J.  S.  C.  I.,  1902,  344  and  British  Patent  10,412,  1901),  who  found  it 
possible  to  increase  the  porosity  of  catalytic  material  by  ignition  with  such  carbo- 
naceous matter,  so  as  to  form  blowholes  or  bubbles  in  the  catalytic  mass. 


64  THE  HYDROGENATION  OF  OILS 

more  red  vapors  depart,  when  the  voluminous  nickel  oxide  which  is 
formed  is  removed  from  the  muffle  and  a  fresh  portion  of  the  solution 
is  introduced. 

In  place  of  cane  sugar  other  varieties  of  sugar  may  be  applied  and 
also  water-soluble  starch,  dextrine,  gum,  tartaric  acid  or  other  water- 
soluble  organic  acid  substances  which  are  rich  in  carbon. 

In  a  similar  manner  the  oxides  of  cobalt  and  iron  or  other  cata- 
lytically-active  oxides  may  be  brought  into  a  voluminous  form.* 

It  is  the  belief  of  Erdmann  f  that  the  oxide  catalysts  are  superior 
to  metal  catalytic  material,  because  the  former  not  only  have  strongly 
marked  catalytic  properties  but  they  are  more  stable  than  the  latter. 
Erdmann  refers  to  prior  investigations  of  Ipatiew  who  worked  with 
various  organic  compounds  other  than  fats,  employing  nickel  oxide 
and  hydrogen  under  very  high  pressure;  while  in  the  present  case 
fatty  material,  it  is  claimed  by  Erdmann,  is  smoothly  hydrogenated 
under  ordinary  atmospheric  pressure.  For  example,  linseed  oil  or 
any  other  fatty  oil  may  be  heated  with  one-half  to  one  per  cent  of 
nickel  oxide,  such,  for  example,  as  may  be  obtained  by  calcining  pure 
nickel  nitrate  at  a  low  red  heat.  The  temperature  of  the  linseed  oil 
is  raised  to  about  255  degrees  and  a  stream  of  hydrogen  is  passed 
through  the  oil  when  it  is  observed  that  the  nickel  oxide  and  oil  mix- 
ture becomes  deep  black  and  the  oxide  appears  to  undergo  subdivision 
and  possibly  transformation  into  a  colloidal  state,  the  solvent  acquiring 
an  ink-like  appearance.  At  the  same  time  hydrogen  is  absorbed  and 
the  oil  is  hydrogenated. 

This  "  colloidal  "  form  of  nickel  oxide  catalyzer,  which  apparently  has 
not  been  observed  with  metallic  nickel,  is  regarded  by  Erdmann  as 
of  great  importance  in  this  art  because  it  enables  a  finely-divided 
catalyzer  of  an  effective  nature  to  be  so  easily  prepared.  When  the 
hardening  process  is  finished  the  nickel  oxide  catalyzer  clots  and 
collects  so  that  it  may  be  separated  readily  from  the  hardened  fat. 

The  analyses  of  the  hardened  products  of  linseed,  peanut  and  sesame 
oil  show  that  by  the  process  an  approximately  pure  glyceride  of  stearic 
acid  is  produced  without  any  trace  of  oxy  fatty  acid  impurity. 

Nickel  soaps  form  in  the  presence  of  free  fatty  acid  only  in  an  in- 
consequential way  to  an  amount  of  about  T£¥  of  1  per  cent  or  so. 
This  slight  amount  is  said  to  remain  along  with  the  catalyzer  in  an 
undissolved  state. 

*  Suboxide  of  nickel  is  prepared  for  catalytic  purposes,  according  to  Bedford 
and  Williams  (J.  S.  C.  I.,  1914,  324),  by  heating  a  mixture  of  nickel  oxide  or  an 
organic  salt  of  nickel  with  oil  in  a  current  of  hydrogen. 

t  Seifen.  Ztg.  (1913),  605. 


THE  BASE  METALS  AS  CATALYZERS  65 

The  whole  hardening  process,  when  pure  hydrogen  is  at  one's  dis- 
posal, is  so  simple  with  reference  to  the  apparatus  required,  and 
operates  so  smoothly  that  the  shifting  from  the  laboratory  experiments 
to  work  on  a  large  scale  is  stated  to  have  offered  no  difficulties. 

In  one  experiment  carried  out  by  Bedford  and  Erdmann  *  3  grams  of  freshly  pre- 
pared nickel  oxide  were  added  to  30  grams  of  cottonseed  oil  and  treated  with  hydro- 
gen at  260°  C.  until  the  oxide  had  become  black  in  color  and  very  finely  divided. 
The  solidifying  point  of  the  fat  was  then  48°  C.  The  mixture  was  cooled  to  185°  C., 
270  cc.  of  cottonseed  oil  added  and  a  strong  current  of  hydrogen  passed  through  the 
oil  and  catalyzer  (maintained  at  185°  C.),  for  one  hour  when  the  solidifying  point 
was  found  to  be  45°  C. 

Another  interesting  question  to  which  reference  has  already  been 
made  is  whether  or  not  nickel  oxide  in  oil  is  reduced  to  metallic  nickel 
by  hydrogen,  and  whether  any  finely-divided  metal  which  might  arise 
in  this  manner  is  a  carrier  of  hydrogen. f 

While  nickel  oxide  (NiO  or  N20)  yields  nickel  in  an  hydrogen  atmos- 
phere at  260  degrees  and  even  in  fact  as  low  as  190  degrees,  the  be- 
havior of  these  bodies,  according  to  Erdmann,  is  very  different  when 
they  are  immersed  in  oil.  In  the  latter  case  the  oil  acts  as  a  protective 
element  and  hinders  or  prevents  complete  reduction.  The  reduction 
goes  no  further  than  the  suboxide  stage,  and  Erdmann  believes  that 
some  sort  of  an  addition  compound  is  formed  with  the  unsaturated  oil. 
If  the  catalyzer  is  removed  from  the  hardened  fat  and  entirely  freed 
from  the  latter  by  extraction  with  benzol,  the  used  catalytic  material 
is  obtained  in  the  form  of  a  soft  black  powder  which  is  more  or  less 
strongly  magnetic,  but  which  does  not  possess  any  conducting  power 
for  electricity. 

A  great  number  of  analyses  have  shown  that  the  nickel  content 
lies  between  nickelous  oxide  and  a  form  of  suboxide  described  by 
Moore. t  Not  the  slightest  trace  of  metallic  nickel  is  found  in  the 
used  catalyzer  if  the  fatty  oil  is  free  from  strongly  reducing  substances 
such  as  aldehydes  or  formic  acid. 

*  Jour.  f.  prakt.  Chem.,  1913,  446. 

t  The  possibility  of  nickel  oxide  and  carbonate  becoming  reduced  during  hydro- 
genation  operation,  so  as  to  actually  yield  a  metallic  catalyzer  similar  to  that  cov- 
ered by  the  Leprince  and  Siveke  basic  patent,  is  considered  by  Mayer  (Seifen.  Ztg. 
(1913),  1224)  who  also  discusses  the  situation  in  Germany  respecting  patented 
processes  of  hydrogenation. 

Professor  Erdmann  (Seifen.  Ztg.  (1913),  1325)  discusses  the  scope  of  the  Le- 
prince and  Siveke  German  Patent  141,029  corresponding  to  the  Normann  British 
Patent  1515,  1903,  especially  with  regard  to  the  use  of  nickel  oxide  catalyzer  in  the 
form  employed  by  Bedford  and  Erdmann. 

t  Chem.  News,  71,  82. 


66  THE  HYDROGENATION  OF  OILS 

The  absence  of  metallic  nickel*  is  rather  definitely  shown  through 
the  indifferent  electrical  conductivity  of  some  used  nickel  oxide  cata- 
lyzer from  which  the  fat  had  been  removed,  the  oxide  being  pressed 
into  block  form  for  the  purposes  of  such  test.  A  control  test  made 
with  catalyzer  which  before  use  had  received  an  addition  of  a  few 
per  cent  of  freshly-reduced  nickel  showed,  under  like  circumstances, 
a  relatively  high  electrical  conductivity.  Also  the  very  different  be- 
havior of  carbon  monoxide  toward  metallic  nickel  and  nickel  oxide 
indicates  the  non-metallic  nature  of  the  used  nickel  oxide  catalyzer. 

So  in  two  ways  it  is  alleged  to  have  been  shown  that  under  normal 
conditions  of  the  process  of  hydrogenation,  nickel  oxide  is  not  reduced 
to  metallic  nickel.  According  to  Erdmann,  after  numerous  compara- 
tive tests,  a  great  advantage  of  the  process  over  those  made  known 
up  to  this  time  has  been  established.  The  fact  that  nickel  oxide  cata- 
lyzers experience  a  partial  reduction  to  nickel  suboxide  brings  up  the 
question  as  to  whether  or  not  the  suboxide  is  the  only  oxide  of  nickel 
which  is  capable  of  transferring  hydrogen  to  unsaturated  compounds. 

In  the  application  of  the  higher  oxide  the  first  phase  of  the  hydro- 
genation which  takes  place  at  250  degrees  is  that  of  the  formation  of 
magnetic  suboxide,  and  the  once-used  nickel  oxide  catalyzer  possesses 
more  marked  activity  than  the  unused.  With  such  a  once-used 
catalyzer  hydrogenation  progresses  with  much  greater  rapidity  and 
also  at  an  essentially  lower  temperature.  After  use  eight  times  the 
nickel  oxide  catalyzer  was  still  active. 

Erdmann  prepared  Moore's  suboxide  through  electrical  reduction 
from  a  solution  of  nickel  potassium  cyanide.  This  he  found  possessed 
the  properties  stated  by  Moore,  namely,  it  was  magnetic,  reduced 
nitric  acid,  developed  hydrogen  with  mineral  acids  and  showed  no 
electrical  conductivity.  The  compound,  both  in  water  and  in  oil, 
showed  colloidal  properties.  When  introduced  into  hot  cottonseed  oil 
it  distributed  itself  through  the  oil  in  the  form  of  a  very  fine  suspen- 
sion which  colored  the  oil  black,  and  treatment  with  hydrogen  at 
210°  C.  indicated  that  the  compound  even  at  that  relatively  low  tem- 
perature was  an  excellent  reduction  catalyzer. 

In  passing,  it  may  be  mentioned  that  other  oxides  besides  nickel 
have  been  found  to  possess  the  property  of  transferring  hydrogen. 

*  Meigen  and  Bartels  (J.  prakt.  Chem.,  1914,  301)  consider  the  views  of  Erdmann, 
regarding  the  formation  of  nickel  suboxide  when  employing  an  oxide  catalyzer,  to 
be  untenable,  and  conclude  that  metaDic  nickel  is  formed  under  the  conditions 
established  by  hydrogenation.  Experimental  studies  in  support  of  this  position 
are  detailed.  From  the  analytical  results,  the  electrical  conductivity  and  the 
observed  formation  of  nickel  carbonyl,  Meigen  and  Bartels  consider  metallic  nickel 
to  be  indicated,  contrary  to  the  views  of  Erdmann. 


THE  BASE  METALS  AS  CATALYZERS  67 

This  has  been  noted  with  copper  and  iron  oxide.  Osmium  tetroxide 
has  been  found  by  Lehmann  to  effect  hydrogenation  while  in  itself 
becoming  converted  into  colloidal  osmium  dioxide. 

A  comparison  has  been  made  by  Erdmann  between  oxide  catalyzers 
and  organic-salt  catalyzers,  such  as  the  formate,  acetate,  oleate  and 
other  similar  salts  which  have  been  studied  in  connection  with  oil 
hardening,  and  Erdmann  has  reached  the  conclusion  that  these  salts' 
do  not  act  directly  as  catalyzers.  In  order  to  effect  hardening  it  is 
necessary  to  break  down  the  organic  salt.  It  does  not  in  itself  possess 
the  property  of  acting  as  a  hydrogen  carrier.  So  long  as  it  remains 
unchanged  no  hydrogenation  takes  place.  As  soon,  however,  as  a 
sufficiently  high  temperature  is  reached,  Erdmann  thinks  these  organic 
nickel  salts,  under  the  influence  of  hydrogen,  are  decomposed  in  such 
a  way  as  to  form  nickel  oxide  and  the  suboxide,  which  latter  possesses 
the  property  of  forming  an  oil  colloid  and  becomes  active  as  a  catalyst. 

Under  some  circumstances  a  mirror  of  metallic  nickel  forms  on  the 
walls  of  the  vessel;  this  occurs  especially  easily  when  nickel  oleate  is 
used,  and  also  has  been  noted  with  nickel  formate  when  the  oil  is 
maintained  at  a  relatively  high  temperature,  approximately  250°  C. 
The  metallic  nickel  which  forms  as  a  mirror  or  otherwise,  it  is  claimed, 
does  not  exert  a  catalytic  action,  but  the  nickel  oxides  which  arise 
and  which  pass  into  the  oil  in  a  finely-divided  condition  are  effective 
catalysts.* 

The  application  of  organic  nickel  salts,  such  as  nickel  formate,  suffers 
the  disadvantage  that  the  action  is  not  immediate,  because  time  is 
required  to  effect  the  decomposition  of  the  formate.  Furthermore, 
there  is  the  loss  in  formic  acid  and  the  costliness  of  regenerating  the 
catalyzer.* 

*  Bohm  (Seifen.  Ztg.  (1912),  737,  Soap  Gazette  and  Perfumer,  1913, 107)  advances 
the  rather  sweeping  view  that  many  of  the  patents  issued  subsequent  to  the  Leprince 
and  Siveke  German  Patent  141,029,  1902,  have  little  or  no  standing.  He  states 
that  operations  involving  changes  in  air  pressure  are  common  expedients  of  organic 
chemistry;  that  spraying  oils  to  secure  intimate  contact  with  gases  is  well  known, 
citing  such  use  in  the  linseed  oil  industry;  and  that  metallic  catalyzers  in  the  col- 
loidal form  may  fall  within  the  definition  of  a  finely-divided  metal.  He,  however, 
regards  the  metal  salt  catalyzers  as  being  independent  of  the  Leprince  and  Siveke 
Patent,  but  expresses  some  doubt  as  to  the  continuance  of  their  use  in  Germany  after 
the  expiration  in  1917  of  German  Patent  141,029. 

The  views  of  Bohm  are  criticized  in  the  Seifensieder  Zeitung  (1912),  1001,  his 
idea  that  almost  all  patents  for  oil  hardening  will  lose  their  value  with  the  expiration 
of  the  Leprince  and  Siveke  Patent  in  1917  being  regarded  as  erroneous.  The 
contrary  is  more  likely  to  take  place,  that  is,  the  value  of  these  processes  will  advance. 
It  is  a  matter  of  surprise  that  Bohm  regards  the  metal  salt  catalyzers  as  independent 
of  the  Leprince  and  Siveke  Patent.  Nickel  formate,  as  well  as  other  salts,  such  as 


68  THE  HYDROGENATION  OF  OILS 

Sabatier  and  Espil  have  studied  the  reduction  by  hydrogen  of  nickel 
oxide  obtained  by  igniting  the  nitrate.  Reduction  takes  place  at 
170°  C.,  at  which  temperature,  after  112  hours,  72  per  cent  were  re- 
duced. Thereafter  the  reaction  progressed  more  slowly  and  after  160 
hours  the  conversion  amounted  only  to  80  per  cent.  These  and  other 
observations  appear  to  disprove  the  claim  made  by  Glaser  that  below 
330°  C.  not  over  50  per  cent  of  nickel  are  reduced  and  that  the  oxide 
Ni20  is  produced.  In  fact,  the  work  of  Sabatier  and  Espil  would  in- 
dicate the  existence  of  a  difficultly  oxidizable  oxide  having  the  formula 
Ni40.* 

Sabatier  and  Espil  in  a  further  investigation  of  the  question  of 
degree  of  reduction  of  nickel  oxide  when  heated  in  the  presence  of 
hydrogen  make  note  f  that  a  careful  calcination  of  nickel  nitrate 
affords  nickel  oxide  which  reduces  to  metallic  nickel  at  a  temperature 
of  155°  C.  without  the  production  of  a  non-reducible  suboxide. 
When  the  oxide  is  calcined  at  a  bright  red  heat  reduction  takes  place 
at  155°  C.,  but  the  action  is  slower. 

An  additional  contribution  to  this  subject  by  Sabatier  and  Espil 
(Comp.  rend.  1914,  668)  indicates  that  sufficient  metallic  nickel  is 
formed  from  the  oxide  in  oil  to  explain  the  catalysis  observed  in  the 
case  of  the  Bedford-Erdmann  process.  Sabatier  and  Espil  use  the  term 
coefficient  of  reduction  to  represent  the  proportion  of  oxide  reduced  per 
hundred  parts.  At  240°  C.  on  three  hours  exposure  to  hydrogen,  an 
oxide  of  nickel  which  had  been  prepared  by  calcination  at  550°  C. 

nickel  lactate,  acetate,  etc.,  proposed  by  Wimmer  and  Higgins,  are  first  broken 
down  into  nickel  oxide  and  acid;  while  under  the  influence  of  heat  and  hydrogen 
the  organic  acid  is  further  decomposed  and  the  nickel  oxide,  at  least  in  part,  appar- 
ently is  reduced  to  metallic  nickel.  Without  the  presence  of  metallic  nickel  hydro- 
genation  is  thought  to  be  scarcely  possible. 

The  decomposition  of  nickel  formate  into  acid  and  metallic  nickel  is  said  to  be 
very  easily  demonstrated  by  a  laboratory  test.  Wimmer  and  Higgins  may  perhaps 
conduct  the  process  so  as  not  to  form  metallic  nickel.  A  serious  disadvantage  exists 
in  the  regeneration  of  the  once-used  contact  material  of  this  character;  for  recon- 
version into  nickel  formate,  acetate  and  other  costly  organic  salts  is  an  expensive 
operation.  The  oxide  catalyzers  likewise  would  be  expected  to  form  metallic  nickel 
during  the  hydrogenation  process,  even  though  the  reduction  be  only  partial.  From 
the  work  of  Ipatiew  such  reduction  apparently  does  not  take  place.  Possibly  the 
envelopment  of  the  molecules  of  oxide  by  oil  hinders  the  reducing  action  of  the 
hydrogen. 

The  doubts  formerly  had  with  regard  to  the  effectiveness  of  oxide  catalysts  have 
now  vanished,  for  during  a  considerable  period  this  contact  material  has  been  used 
for  hardening  oils  on  the  large  scale.  A  reduction  of  the  oxides  to  the  metallic 
state  has  not  been  observed  under  these  circumstances. 

*  Chem.  Ztg.  (1913),  1121. 

t  Chem.  Ztg.  (1913),  1549. 


THE  BASE  METALS  AS  CATALYZERS  69 

showed  a  coefficient  of  reduction  of  93,  while  oxide  which  had  been 
ignited  at  a  bright  red  heat  exhibited  a  coefficient  of  32.8.  (These 
figures  relate  to  the  dry  oxide  not  in  oil.)  At  155°  C.  on  96  hours  ex- 
posure to  hydrogen,  a  light  oxide  gave  a  reduction  coefficient  of  56  and 
a  calcined  oxide  was  found  to  have  a  coefficient  of  only  2.5.  The  rate 
of  reduction  was  found  to  be  somewhat  accelerated  by  increase  in  the 
rate  of  flow  of  hydrogen  over  the  oxide  mass.  At  240°  C.,  with  a  rate 
of  flow  of  hydrogen  of  6  cu.  cm.  per  minute  the  coefficient  was  44.5,  at 
17  cu.  cm.  the  coefficient  increased  to  65  and  at  24  cu.  cm.  the  coefficient 
became  77.5.  Sabatier  and  Espil  note  that  elevation  of  the  temperature 
greatly  increases  the  speed  of  reduction.  At  220°  C.  with  oxide  of 
nickel,  the  following  coefficients  were  obtained. 

1  hour 14.9 

4  hours 57 . 6 

5 . 5  hours 77 . 4 

6.5  hours 78.0 

7.5  hours 79.9 

22  hours 99.6 

At  250°  C.  the  coefficients  were  found  to  be  as  follows: 

\  hour 30.0 

1  hour 52.0 

1.5  hours 78.9 

2  hours 87.0 

2.5  hours 92.5 

3  hours 95.3 

15  hours 100.0 

Between  190°  to  240°  C.  the  speed  of  reduction  is  an  exponential  func- 
tion of  the  temperature.  The  reduction  of  nickel  oxide  at  175°  C. 
gave  a  coefficient  of  10  and  on  treating  this  product  with  carbon  mon- 
oxide at  50°  C.  nickel  carbonyl  was  obtained.  Sabatier  and  Espil  con- 
clude that  a  suboxide  is  formed  by  reduction  in  this  manner,  having 
the  composition  NLjO,  corresponding  to  the  coefficient  75.  This  sub- 
oxide  is  not,  however,  irreducible  but  is,  as  stated  above,  more  slowly 
reduced  than  the  protoxide. 

Dry  hydrogen  has  been  found  to  reduce  the  oxide  better  than  moist 
gas  and  in  practice  it  is  recommended  that  the  hydrogen  employed  for 
reduction  purposes  be  freed  from  moisture  before  use.* 

t  Sabatier  and  Espil  have  observed  that  moist  hydrogen  is  at  least  as  active  as 
dry  hydrogen  in  the  hydrogenation  of  benzene  and  phenol  (Bull.  Soc.  Chim.,  1914, 

228). 


70 


THE  HYDROGENATION  OF  OILS 


The  rate  of  hardening  of  cottonseed  oil  by  nickel  and  nickel  oxide 
catalyzers  has  been  investigated  by  Meigen  and  Bartels  (J.  prakt. 
Chem.,  1914,  293)  and  their  results  are  shown  in  Fig.  43.  Curves  1,  2 
and  3  were  derived  with  metallic  nickel  at  170°  C.,  and  4  and  5  with 
nickel  oxide  at  250°  to  255°  C.  The  amount  of  catalyzer  in  all  cases 
corresponded  to  two  per  cent  of  nickel  oxide.  No.  1  was  obtained  with 
nickel  prepared  from  the  carbonate,  No.  2  from  reduced  oxide  and  No. 
3  from  a  commercially-used  catalyzer.  The  oxide  employed  in  Nos.  4 
and  5  was  obtained  by  ignition  of  the  nitrate.  These  curves  indicate 
a  slower  action  for  the  oxide,  which  Meigen  and  Bartels  attribute  to  the 
time  required  for  preliminary  reduction  of  the  oxide  after  its  addition 
to  the  oil,  and  before  actual  hydrogenation  of  the  oil  occurs. 

Free  oleic  acid  can  be  hardened  very  easily  by  means  of  a  nickel 
oxide  catalyzer,  according  to  Bedford  and  Erdmann*  Nickel  oleate 
forms  only  in  slight  amount. 

Pure  nickel,  obtained  by  reduction  of  the  nitrate,  according  to 
Chem.  Fabr.  auf  Actien,f  is  inactive  for  the  purpose  of  converting 

borneol  into  camphor;  if,  however,  a 
small  quantity  of  sodium  carbonate 
be  added  to  the  nitrate  before  re- 
duction, a  very  active  product  is 
obtained;  a  similar  mixture  is  ob- 
tained by  adding  0.17  per  cent  of 
pure  sodium  oxide  to  the  nickel; 
other  bases  or  salts  which  are  not 
readily  reduced  at  a  red  heat  may 
be  used  in  place  of  sodium  oxide. 
Further,  if  a  small  quantity  of  cer- 
tain other  metals  is  introduced  into 
the  nickel,  the  mixture  will  have 
a  very  powerful  catalytic  action. 
Mixtures  of  6.7  per  cent  of  cobalt  or  copper  with  93.3  per  cent  of  nickel 
may  be  used;  they  are  obtained  by  the  reduction  of  the  mixed  ni- 
trates. The  process  is  not  confined  to  the  use  of  nickel;  it  is  stated 
that  other  metals  possessing  catalytic  action  can  be  used  with  equal 
effect. 

By  a  method  somewhat  similar  to  that  of  Bedford  and  Erdmann  the 
proposal  comes  from  Kast  t  to  prepare  catalysts  in  a  finely-divided  volu- 

*  Jour.  f.  prakt.  Chem.,  1913,  450. 

t  French  Patent  401,876,  April  8,  1909;  German  Patents  219,043  and  219,044, 
1908. 

t  U.  S.  Patent  1,070,138,  Aug.  12,  1912. 


60  90  120 

FIG.  43. 


THE  BASE  METALS  AS  CATALYZERS  71 

minous  condition  by  heating  the  trinitrophenol  salt  of  a  heavy  metal: 
These  salts  are  combustible  and  when  ignited  they  expand  greatly, 
so  the  resulting  ashes  (metal  or  metal  oxide)  are  found  to  be  in  a  volu- 
minous, spongy  form.  Kast  claims  that  the  usual  procedure  of  pre- 
cipitating a  salt  solution  (with  or  without  a  carrier)  yields  a  coarse 
crystalline  precipitate,  and  that  reduction  by  heating  in  a  reducing  gas 
slags  the  precipitate  in  consequence  of  which  the  catalytic  effectiveness 
is  considerably  diminished.  To  avoid  danger  of  an  explosion  when 
decomposing  the  trinitrophenol  compound  by  ignition  Kast  adds  oil 
or  tar  as  a  diluent.  He  also  recommends  for  this  purpose  nitrate  of 
ammonia,  as  this  salt  evolves  large  quantities  of  gas  on-  heating  and 
leaves  no  residue.  The  formation  of  slag  which  Kast  objects  to  in 
ordinary  reduction  seemingly  would  be  aggravated  when  a  salt  of 
trinitrophenol  is  burned  under  these  conditions. 

The  hydrogenation  of  unsaturated  fatty  acids  and  their  esters 
may  be  effected,  according  to  deKadt,*  by  means  of  hydrogen  in  the 
presence  of  a  catalyst  consisting  of  a  soap  of  a  heavy  metal  or  of  a  noble 
metal,  made  from  a  fat  or  fatty  acid  having  a  melting  point  higher  than 
that  of  the  saturated  compound  to  be  produced.  For  example,  the 
nickel  soap,  or  preferably  a  mixture  of  the  nickel  and  iron  or  copper 
soaps  of  the  fatty  acids  of  stearine  or  Japan  wax,  is  dried  and  powdered, 
and  can  then  be  intimately  mixed  with  the  oil  to  be  hydrogenated. 
After  hydrogenation  the  oil  is  left  quiescent  at  a  temperature  above  its 
melting  point,  when  the  soap  particles  will  agglomerate  and  settle  on 
cooling.  If,  however,  the  oil  is  kept  in  motion  and  filtered,  the  soap 
does  not  pass  through  the  filter.  It  is  stated  that  this  process  is  more 
efficient  than  when  metallic  catalysts  are  used,  owing  to  the  more 
intimate  contact  between  the  catalyst  and  oil  or  fat  which  is  here 
obtained. 

Basic  compounds  of  high  molecular  fatty  acids  with  certain  of  the 
heavy  metals  are  proposed  as  catalyzer  formative  material  by  Hausa- 
mann.f  The  compounds  dissolve  in  the  oil  undergoing  treatment 
and  in  the  presence  of  hydrogen  afford  active  catalytic  bodies.  The 
temperatures  employed  range  from  100°  to  180°  C.  After  the  oil  has 
been  hardened  it  may  be  treated  with  dilute  acid  to  remove  the 
catalyzer.  J 

The  employment  of  a  basic  salt  of  a  heavy  metal  (nickel  or  copper) 
with  a  fatty  acid  is  recommended  by  De  Nordiske  Fabriker  De-No-Fa 
Aktieselskap  as  a  catalytic  material  in  the  hardening  of  fats  or  fatty 

*  British  Patent  18,310,  Aug.  9,  1912. 

t  Zeitsch.  f.  angew.  Chem.  (1914),  63,  No.  7. 

\  See  also  Seifen.  Ztg.  (1914),  7. 


72 


THE  HYDROGENATION  OF  OILS 


acids.  About  0.4  per  cent  of  the  metallic  compound  is  used  and  the 
hydrogenation  takes  place  at  temperatures  between  100°  C.  and 
180°  C.* 

Organic  compounds  of  metals,  such  as  metallic  salts  of  organic 
acids,  are  employed  by  Wimmer  and  Higgins  f  as  catalytic  agents  in 
the  reduction  or  hydrogenation  of  various  organic  compounds;  thus 
the  copper,  iron,  nickel  or  cobalt  salts  of  formic,  acetic  or  lactic  acid 

may  be  employed.  The  ad- 
vantage of  these  compounds  is 
that  they  can  readily  be  mixed 
with  the  compound  to  be  re- 
duced, either  in  the  form  of  a 
solution  or  as  an  "  emulsion  "; 
thus  the  compound  may  be 
emulsified  with  the  catalyst 
and  at  the  same  time  treated 
with  hydrogen.  It  is  stated 
that  hydrogenation  may  be  ac- 
celerated either  by  using  the 
hydrogen  under  pressure,  or 
by  impregnating  the  compound 

to  be  reduced  with  hydrogen, 
and  ^  bri  ;  jt  into  ;n_ 

-it. 
hydrogen  on  nickel  resinate  dissolved  in   timate   contact  With  the  cata- 

the  oil.  x  100.  lyst.  One  detailed  example  is 

given  in  the  specification,  de- 
scribing the  treatment  of  100  grams  of  cottonseed  oil  with  hydrogen 
in  presence  of  1  to  5  grams  of  nickel  formate  at  a  temperature  of  170° 
to  200°  C. 

Wimmer  makes  the  statement  that  these  organic  salts  are  not 
reduced  to  the  metallic  condition  during  hydrogenation. | 

Bedford  and  Erdmann  §  state  that  nickel  formate  yields  nickel  sub- 
oxide  at  210°  C.,  while  metallic  nickel  is  formed  at  250°  C.,  and  that 
nickel  acetate,  oleate  and  linoleate  behave  in  a  similar  manner. 

Higgins  ||  uses  nickel  or  zinc  formate  in  the  reduction  of  organic 
compounds  without  the  application  of  gaseous  hydrogen. 

Several  other  methods  of  producing  catalyzers  have  been  the  sub- 

*  J.  S.  C.  I.,  1914,  324. 

t  French  Patent  441,097,  March  8,  1912. 

J  Seifen.  Ztg.  (1913),  1301. 

§  Zeitsch.  f.  ang.  Chem.  ref.  (1913),  751. 

II  Chem.  Ztg.  Rep.  (1913),  680;  British  Patent  23,377,  Oct.  12,  1912. 


FIG.  44.  —  Photo-micrograph  of  nickel  pre- 
cipitated in  cottonseed  oil  by  the  action  of 


THE  BASE  METALS  AS  CATALYZERS  73 

ject  of  the  patents  as,  for  example,  that  to  Crosfield  *  in  accordance 
with  which  kieselguhr  and  the  like  is  impregnated  with  a  solution 
of  nickel  sulfate  and  the  impregnated  material  treated  with  alkali 
hydrate  to  precipitate  nickel  hydrate  in  and  on  the  porous  material. 
The  product  is  then  well  washed,  dried  and  reduced.  If  kieselguhr 
is  used  the  powder  should  contain  about  30  per  cent  of  metallic  nickel. | 
A  similar  procedure  is  the  subject  of  a  patent  to  Kayser.J  In  this 
case,  however,  the  nickel  sulfate  or  other  nickel  salt  in  concentrated 
solution  may  be  used  in  an  amount  to  saturate  kieselguhr  while  leaving 
it  in  an  apparently  dry  condition,  when  it  is  incorporated  with  a  molec- 
ular proportion  of  powdered  carbonate  of  soda  and  the  mixture  thrown 
into  boiling  water,  dried  and  reduced. 

Kayser  states  that  there  are  various  known  ways  for  producing  metallic  powders  in 
a  state  of  fine  division.  Nickel  powder,  which  for  many  purposes  is  recognized  as 
the  most  potent  catalyzer  technically  available,  is,  for  example,  most  conveniently 
produced  by  acting  upon  such  nickel  compounds  as  the  chloride,  oxide,  hydrate  or 
carbonate  at  an  adequate  temperature  with  hydrogen.  The  catalytic  energy  of 
such  a  powder,  however  carefully  prepared,  he  says,  is  at  best  an  uncertain  quantity; 
frequently  it  is  feeble,  as  sometimes,  for  no  conclusive  reason,  it  is  altogether  lack- 
ing. Furthermore,  powder  thus  produced  is  specifically  heavy  and  he  claims  can- 
not be  easily  kept  in  suspension  in  a  liquid  medium  like  oil,  when  that  is  desired, 
nor  can  it,  since  it  forms  an  almost  impervious  sediment,  be  readily  separated  and 
recovered  from  such  liquid  medium  by  a  contrivance  like  the  filter  press.  The  same 
objections,  he  says,  apply  to  nickel  powder  prepared  by  other  means;  and,  in  the 
endeavor  to  improve  on  these,  Kayser  brings  a  compound  of  nickel,  such  as  the 
nitrate,  oxide,  hydrate  or  carbonate,  into  intimate  contact  with  an  inert,  absorptive 
and  comparatively  bulky  mineral  substance,  such  as  kieselguhr  and  infusorial  earth, 
dries  and  comminutes  the  product,  and  reduces  the  powder  thus  produced.  In  one 
case  he  saturates  kieselguhr  with  a  solution  of  nickel  nitrate,  dries  the  mixture, 
employing  in  the  case  of  the  nitrate  sufficient  heat  to  expel  the  nitric  acid,  grinds 
the  resulting  product  and  reduces  with  hydrogen.  Another  way  is  to  permeate 
or  saturate  kieselguhr  with  a  solution  of  nickel  chloride,  nickel  sulfate  or  other 
soluble  nickel  salt,  enter  the  resulting  product,  with  or  without  previous  drying,  into 
a  boiling  solution  of  carbonate  or  hydrate  of  soda  or  other  suitable  precipitant,  remove 
the  soluble  salts,  formed  by  washing,  dry  and  comminute  the  residue,  and  reduce 
it  as  before.  A  third  and  preferred  method,  as  stated,  is  to  saturate  the  kieselguhr 
with  a  solution  of  nickel  chloride,  nickel  sulfate  or  other  nickel  salt,  using  so  much 
solution  only  as  will  leave  the  kieselguhr  in  an  apparently  dry  and  freely  workable 

*  British  Patent  30,282,  1910. 

t  Ubbelodhe  and  Woronin  (Petroleum  (1911),  7,  9)  prepared  a  catalyzer  by  crush- 
ing a  plate  of  porous  clay  (which  had  been  ignited)  to  form  particles  of  about  the 
size  of  peas.  Nickel  nitrate  was  melted  and  heated  until  water  vapor  ceased  to  be 
evolved.  Then  the  clay  particles  were  added  and  the  mass  was  stirred  and  strongly 
heated  to  expel  the  oxides  of  nitrogen.  This  step  was  followed  by  reduction  with 
hydrogen  at  360°  C. 

t  U.  S.  Patent  1,004,034,  Sept.  26,  1911. 


74  THE  HYDROGENATION  OF  OILS 

condition,  incorporate  a  molecular  proportion  of  powdered  carbonate  of  soda  or 
other  powdered  precipitant,  throw  the  mixture  with  constant  stirring  into  boiling 
water,  remove  the  soluble  salts  formed  by  washing,  dry  and  comminute  the  mixture, 
and  reduce  as  before. 

To  develop  the  highest  catalytic  efficiency,  Kayser  states  that  the  kieselguhr  should 
become  evenly  and  completely  coated  and  permeated,  plated  as  it  were  with  a  film 
of  metal,  and  that  a  catalyzer  composed  of  one  to  two  parts  by  weight  of  metallic 
nickel  and  four  parts  by  weight  of  kieselguhr  has  however  proved  very  effective  in 
saturating  fats  and  oils  by  means  of  hydrogen.  The  author  can  see  no  advantage 
in  permeating  or  impregnating  the  interior  canals  of  the  carrier  with  catalytic  metal 
when  the  catalyst  is  to  be  used  for  hydrogenating  fatty  oils.  The  porous  support 
used  by  Sabatier  and  Senderens,  to  be  sure,  was  impregnated  with  reduced  nickel, 
but  these  investigators  directed  their  attention  to  the  hydrogenation  of  readily 
volatile  substances,  capable  of  diffusing  into  the  interior  of  the  nickel-laden  porous 
material. 

Seeking  to  overcome  the  disadvantage  of  ready  oxidation  in  the  air 
possessed  by  normal  catalytic  nickel,  Kayser  *  reduces  the  nickel 
oxide  or  equivalent  material  at  a  temperature  of  500°  to  600°  C.  and 
then  passes  through  the  reduced  material  a  brisk  current  of  carbonic 
acid  until  the  escaping  gas  proves  no  longer  inflammable.  By  this 
method  it  is  claimed  that  a  catalyzer  is  secured  which  will  remain  per- 
fectly cool  on  exposure  to  the  air  and  even  may  be  exposed  for  days 
without  losing  any  of  its  catalytic  energy,  a  result  which  probably,  is 
due  to  elimination  of  occluded  hydrogen.! 

Wilbuschewitch  J  proposes  to  secure  more  rapid  reduction  of  cata- 
lyzer by  agitating  it  in  the  presence  of  hydrogen  in  a  heated  rotary 
drum.  The  temperature  during  the  treatment  is  stated  to  be  500°  C. 
Wilbuschewitch  §  has  patented  a  process  of  regenerating  spent  cata- 
lysts of  the  nickel  type,  involving  extraction  with  benzene,  treating 
with  alkali  solution,  acidifying,  treating  with  sodium  carbonate  solu- 
tion and  reducing. 

The  recovery  of  catalytic  material  is  described  by  Naamlooze 
Vennootschap,  Ant.  Jurgen's  Vereenigde  Fabrieken  in  British  Patent 
27,233,  1913.11  The  catalyzer  is  freed  from  organic  matter  by  heating 
in  a  current  of  air,  the  material  is  treated  with  an  acid  to  dissolve 
metal  from  its  insoluble  carrier  and  the  metal  is  then  precipitated  on 
the  same  carrier. 

*  U.  S.  Patent  1,001,279,  Aug.  22,  1911. 

f  The  Bremen-Besigheimer  Olfabriken  (Seifen.  Ztg.  (1913),  1007)  recommend 
the  exposure  of  catalytic  material  to  an  atmosphere  of  carbon  dioxide,  or  inert  gases. 
The  catalyzers  produced  in  this  manner  are  stated  to  be  permanent  and  to  possess 
great  activity. 

t  U.  S.  Patent  1,016,864,  Feb.  6,  1912. 

§  U.  S.  Patent  1,022,347,  April  2,  1912. 

II  Seifen.  Ztg.  (1914),  169. 


THE  BASE  METALS  AS  CATALYZERS 


75 


Bedford  and  Erdmann  *  treated  a  quantity  of  used  nickel  oxide  cata- 
lyzer with  dilute  sulfuric  acid.  Hydrogen,  accompanied  by  hydro- 
carbons of  disagreeable  odor,  was  evolved.  A  carbonaceous  residue 
amounting  to  6  or  7  per  cent  remained  after  treatment  with  the  acid. 
Nickel  oxide  has  been  found  to  take  up  silica  when  used  repeatedly  as  a 
catalyzer.  The  same  absorption  of  silica  also  occurs  with  palladium. 


FIG.  45 


Wilbuschewitsch,  in  U.  S.  Patent  1,029,901,  of  June  18,  1912,  de- 
scribes a  process  of  making  a  catalyst  in  which  he  takes,  for  example, 
nickel  sulfate  in  the  form  of  a  solution  of  strength  of  10  to  14  degrees 
Baume,  mixing  this  with  about  double  its  weight  of  an  inorganic 
substance  such  as  clay,  asbestos,  pumice  stone,  kieselguhr  or  the  like, 
from  which  all  soluble  matter  has  been  removed  by  treatment  with  an 
acid.  The  mixture  is  then  treated  with  carbonate  of  soda  to  convert 
the  metal  salt  into  a  carbonate.  The  composition  is  heated  to  about 
500°  C.  so  as  to  transform  the  carbonate  into  the  oxide.  Reduction 
with  hydrogen  is  then  carried  out  and  the  product  is  ground  with  oil 
until,  as  the  patentee  states,  a  strongly  viscous  liquid,  similar  in 
character  to  an  emulsion,  is  produced. 

An  apparatus  employed  by  Wilbuschewitsch,  f  Fig.  45,  for  the  re- 

*  Jour.  f.  prakt.  Chem.,  1913,  444. 

t  U.  S.  Patent  1,029,901,  June  18,  1912.   • 


76  THE  HYDROGENATION  OF  OILS 

duction  of  nickel  compounds  consists  of  a  cylindrical  drum  b  mounted 
to  rotate  on  rollers  m  and  provided  with  a  heating  jacket  o.  The 
material  is  charged  into  the  drum  through  an  inlet  opening  n.  To  one 
of  the  end  plates  of  the  drum  a  tubular  shaft  c  is  secured  which,  with 
its  free  end,  is  guided  in  a  stuffing  box  k  supported  in  a  lateral  stud  of  a 
tubular  receptacle  d.  On  the  shaft  a  spur  gear  q  is  mounted  which  is 
in  mesh  with  a  pinion  qi  adapted  to  be  rotated  by  means  of  a  belt 
pulley  r.  By  means  of  the  gearing  qf,  q  the  drum  b  is  slowly  rotated, 
and  during  such  rotation  it  is  heated  to  about  500°  C.  Hydrogen  is 
then  forced  into  the  drum  through  a  pipe  a  located  coaxially  within 
the  hollow  shaft  c  and  connected  at  one  end  to  a  tube  i.  The  hydrogen 
is  passed  through  the  material  to  be  reduced,  and  from  the  latter  it 
is  successively  conducted  through  an  automatically  operating  dust 
collector  9  connected  to  the  retort,  a  cooling  worm  /  and  purifying 
vessels  g,  g'  containing  respectively  acid  and  caustic  soda  lye,  or  a 
similar  purifying  medium.  After  thus  being  regenerated  it  is  returned 
by  means  of  a  pump  h.  The  water  produced  by  the  reduction  is  con- 
densed in  the  coil  /  and  is  dropped  from  the  coil  /  into  the  vessel  d 
from  which  it  is  withdrawn  through  an  overflow  e.  The  dust  collector 
9  by  means  of  which  the  hydrogen  escaping  from  the  drum  is  pre- 
vented from  carrying  along  particles  of  dust  is  constructed  in  the  form 
of  a  worm  conveyor  I.  The  dust  moves  through  the  hollow  shaft  c  in 
the  direction  of  the  gas  flow  and  owing  to  the  difference  in  the  speed 
of  the  gas  and  dust  the  latter  is  deposited  on  the  bottom  of  the  shaft  c, 
and  is  conveyed  back  into  the  retort  by  the  worm  I. 

A  procedure  noted  in  connection  with  Crosfields  &  Sons,  Ltd.,  vs. 
Techno-Chemical  Laboratories,  Ltd.,*  disclosed  as  apparatus  a  cylin- 
drical autoclave  1  meter  high  and  f  meter  in  diameter  (inside  measure- 
ments), with  a  steam  jacket,  and  fitted  with  a  non-conducting  lining 
of  unknown  material.  Nine  kilograms  of  cotton  oil  were  pumped 
into  the  autoclave,  and  288  grams  of  a  composition,  containing  a 
catalytic  agent,  were  used  and  were  mixed  with  the  oil  prior  to 
the  introduction  of  the  mixture  into  the  autoclave.  The  autoclave 
was  then  filled  with  hydrogen  from  a  cylinder  to  a  pressure  of  15 
atmospheres.  During  the  operation  the  pressure  varied  from  time 
to  time  according  to  the  absorption  of  hydrogen.  A  mechanically 
driven  circulation  pump  was  connected  with  the  autoclave  both  by 
its  suction  and  delivery  conduits.  By  means  of  a  pump  and  a  jet 
for  spraying,  a  mixture  of  oil  and  composition  containing  the  catalytic 
agent  was  drawn  from,  and  forced  back  into,  the  autoclave.  The 
iodine  absorption  was  not  determined.  The  composition  containing 

*  British  Official  Journal  Supplement,  June  18,  1913,  301. 


THE  BASE  METALS  AS  CATALYZERS  77 

the  catalytic  agent  was  prepared  from  a  salt  of  nickel.  The  catalyst 
employed  was  prepared  as  follows:  About  1J  kilograms  of  nickel 
sulfate  were  dissolved  in  3  liters  of  water,  and  the  same  weight  of 
sodium  carbonate,  dissolved  in  the  same  quantity  of  water,  and  at 
about  70°  to  80°  C.  was  added  to  the  nickel  sulfate,  which  was  at 
60°  to  70°  C.  The  mixture  was  stirred  for  1J  to  2  hours,  and  the  pre- 
cipitate was  filtered  off  and  washed  with  distilled  water  at  about  25°  C. 
for  60  to  70  hours  alternately  in  tanks  and  filter  press.  A  small  sample 
was  dried  and  tested  to  ascertain  that  the  precipitate  had  been  suffi- 
ciently washed.  The  washed  precipitate  was  dried  in  hot  air  at  80° 
to  85°  C.,  and  was  calculated  to  weigh  720  grams.  It  was  then  roasted 
in  a  pan  for  about  15  minutes  over  an  open  Bunsen  gas  burner,  and 
the  weight  after  roasting  was  calculated  to  be  about  380  grams.  The 
product  was  heated  to  about  300°  C.  for  about  6  minutes  in  a  current 
of  hydrogen  in  revolving  glass  tubes  slightly  inclined,  the  precipitate 
being  introduced  at  the  higher  end  and  through  a  spiral  glass  tube, 
and  the  hydrogen  at  the  lower  end.  The  product,  which  weighed  288 
grams,  was  directly  introduced  into  a  small  quantity  of  oil,  which  was 
mixed  with  the  9  kilos  the  following  day. 

Catalyzers  said  to  possess  high  activity  are  produced  by  mixing 
with  oil  a  base-metal  compound  of  an  easily-reducible  character  and 
yielding  the  catalytic  metal  on  reduction,  heating  and  bringing  a 
reducing  gas  under  pressure  into  contact  with  this  mixture.* 

Nickel  carbonyl  is  employed  by  Franck  f  to  form  catalytic  material 
by  precipitation  of  nickel  from  the  carbonyl  in  an  oil  menstruum  in  the 
presence  of  solid  material.  The  latter  may  be  kieselguhr  or  nickel 
or  copper  oxides  or  reducible  metallic  salts.  The  solid  material  is 
heated  with  the  oil  and  nickel  carbonyl  conducted  into  the  mixture. 

Eldred  J  does  not  regard  a  finely-divided  catalyst  as  desirable  as 
one  having  a  catalytic  metal  welded  to  a  heat-conducting  support. 
He  states  that  since  the  amount  of  such  catalytic  action  performed 
in  a  given  time  unit  in  a  body  of  gas  is  strictly  proportionate  to  the 
exposed  surface  of  catalyzing  metal,  it  is  customary  to  use  such  metals 
in  finely-divided  form,  sometimes  as  masses  of  powder  and  sometimes 
as  powders  adhering  to  and  held  by  inert  porous  materials,  such 
as  asbestos,  glass  wool  and  the  like,  but  that  these  expedients  while 
giving  great  surface  to  a  given  amount  of  metal  do  not  give  a  pro- 
portionately great  exposure  of  such  metal  to  the  gases  or  vapors  to 
be  treated.  It  is  substantially  impossible  to  drive  or  distribute  gases 

*  Seifen.  Ztg.,  1913,  1298. 
t  Seifen.  Ztg.,  1913,  1271. 
I  U.  S.  Patent  1,043,580,  Nov.  5,  1912. 


78  THE  HYDROGENATION  OF  OILS 

uniformly  throughout  a  body  of  powder,  and  in  passing  gases  over  a 
body  of  such  powder  it  is  substantially  only  the  top  layers  of  the 
powder  which  display  a  maximum  activity,  underlaying  layers  not 
functioning  to  any  great  extent.  Use  of  very  thin  layers  of  powder 
of  course  necessitates  unduly  extended  shelf  surface.  Eldred  observes 
that  nearly  all  catalyses  are  exothermic  reactions,  heat  being  developed 
by  the  action,  and  frequently  the  amount  of  heat  is  rather  large.  And 
as  it  is  usually  desirable  to  work  within  comparatively  narrow  tem- 
perature limits,  keeping  and  maintaining  the  catalytic  metal  within  a 
few  degrees  of  some  definite  temperature,  this  evolution  of  heat  may 
become  a  serious  matter.  Nearly  all  the  catalytically  acting  metal's 
in  the  form  of  powders  are  relatively  poor  conductors  of  heat.  When, 
for  example,  platinum  is  distributed  through  a  mass  of  such  a  heat 
insulator  as  asbestos,  it  is  very  hard  to  prevent  the  accumulation  of 
reaction  heat  in  the  metal.  Hence  Eldred  proposes  a  catalytic  body 
comprising  the  catalytic  metal  in  the  form  of  a  very  thin  continuous 
layer  or  film  supported  by  masses  of  better  heat-conducting  metals 
weld-united  to  such  layer  or  film  and  therefore  in  absolute  metallic 
union  therewith  so  that  by  controlling  the  temperature  of  the  carrying 
metal  the  temperature  of  the  film  or  layer  can  also  be  controlled.  A 
catalyst  may  be  made  by  welding  a  sheath  or  coating  of  platinum  on  a 
billet  of  copper  or  steel  and  "  coextending  "  the  joined  metals  to  form 
wire  or  sheet  metal.  If  3  to  10  per  cent  of  platinum  be  placed  on  the 
original  billet  and  coextension  be  performed  with  care,  the  wire,  sheet 
or  leaf  metal  formed  will  also  have  3  to  10  per  cent  of  platinum,  but 
this  thickness  in  such  coextended  ware  will  correspond  to  an  extremely 
tenuous  layer.  Cobalt  and  nickel  may  be  united  to  steel  or  copper 
billets,  and  the  duplex  or  compound  billets  extended  in  similar  manner 
to  produce  catalysts  having  film  coatings  of  cobalt  or  nickel.  The 
cobalt  or  nickel  may  be  united  to  the  underlying  core  metal  directly 
or  through  a  linking  layer  of  another  metal  such  as  gold,  silver  or 
copper.  Eldred  mentions  the  cobalt  and  nickel  catalyzers  as  useful 
in  hydrogenation  reactions. 

In  the  preparation  of  a  catalytic  body  Ellis  *  recommends  the  use 
of  wood  charcoal  which  possesses  the  property  of  absorbing  or  occlud- 
ing hydrogen  and  when  incorporated  with  nickel  or  other  metal  catalyst 
serves  as  an  activator  and  storehouse  of  hydrogen.  If  nickel  is  used, 
a  ratio  of  one  part  of  metal  to  four  parts  of  charcoal  is  best  not  ex- 
ceeded. The  metallic  compound  may  be  precipitated  more  or  less 
on  the  surface  of  the  charcoal  particles  by  wetting  the  latter  with  a 
solution  of  a  precipitant  and  adding  a  solution  of  a  nickel  salt.  Pre- 
*  U.  S.  Patent  1,060,673,  of  May  6,  1913. 


THE  BASE  METALS  AS  CATALYZERS  79 

cipitation  under  these  conditions  is  largely  external.  Exposure  of 
the  composition  to  the  air  after  reduction  is  to  be  avoided.* 

Miiller  |  finds  the  catalytic  activity  of  iron  and  nickel,  especially  in 
connection  with  processes  for  the  introduction  of  hydrogen  into  gly- 
cerides  of  unsaturated  fatty  acids,  is  considerably  augmented  and 
caused  to  resemble  in  activity  the  catalytic  properties  of  the  noble 
metals,  such  as  palladium,  if  the  former  metals  after  ignition  in  hydro- 
gen are  heated  in  a  stream  of  carbonic  acid  gas  in  order,  apparently, 
to  destroy  the  metal  hydrides  which  are  formed  and  convert  the  cata- 
lyzer into  the  pure  metal.  Muller  says  the  process  also  makes  pos- 
sible the  elimination  of  finely-divided  catalyzer,  whose  production  and 
application  the  patentee  states  is  accompanied  with  many  difficulties, 
and  its  replacement  by  coarse  fragments  of  metal,  such  as  filings  and 
shavings  of  iron,  nickel  and  copper,  first  igniting  the  latter  in  hydrogen 
and  then  in  carbonic  acid  gas.  He  states  that  common  iron  filings 
caused  a  reduction  of  the  iodine  number  of  only  2|  per  cent  in  two 
hours,  while  using  filings  which  had  been  treated  with  carbon  dioxide 
the  iodine  number  was  reduced  25  per  cent. 

When  nickel  hypophosphite  solution  is  boiled,  metallic  nickel  is 
precipitated,  under  some  conditions  as  thin  metallic  leaves;  under 
other  conditions  as  a  fine  powder.  The  latter  form  acts  catalytically 
on  sodium  hypophosphite  in  solution  giving  acid  sodium  phosphite 
with  evolution  of  hydrogen.  The  powder  form  is  obtained  by  dis- 
solving 20  grams  nickel  sulfate  in  100  cc.  water,  heating  on  a  water 
bath,  introducing  in  one  addition  70  grams  sodium  hypophosphite 
and  stirring.  At  the  end  of  one  hour  reduction  is  complete.  Dis- 
tilled water  is  added,  the  nickel  material  is  allowed  to  settle  and  is 
washed  by  decantation.J  Palladium  prepared  in  a  somewhat  similar 
manner  decomposes  sodium  hypophosphite  very  effectively.§ 

On  account  of  the  relatively  low  degree  of  sensitiveness  of  nickel 
oxide  catalyzers  to  the  usual  catalyzer  poisons  Erdmann  ||  was  able  to 
readily  hydrogenate  Japanese  fish  oil  containing  a  high  content  of  free 
fatty  acid  and  also  certain  sulfur-containing  oils,  such  as  Egyptian 
cottonseed  oil. 

If  the  hardening  operation  is  interrupted  before  the  reaction  is  com- 

*  See  also  Ellis,  U.  S.  Patent  1,088,673,  Feb.  24,  1914. 

t  Seifen.  Ztg.  (1913),  747;  French  Patent  540,703  (1912);  British  Patent  22,092, 
Sept.  28,  1912,  to  Muller  Speisefettfabrik. 

I  The  author  has  noted  that  this  precipitated  nickel  material  is  catalytic  and 
readily  acts  to  harden  cottonseed  oil  at  a  temperature  of  210°  C.,  or  thereabouts, 
with  hydrogen  at  atmospheric  pressure. 

§  Breteau,  Bull.  Soc.  Chim.  (1911),  9,  515-519. 

II  Chem.  Ztg.,  1913,  1142,  1173  and  1195. 


80  THE  HYDROGENATION  OF  OILS 

plete,  and  the  catalyzer  collected  by  centrifuging,  extraction  with 
benzol  or  other  solvents  shows  the  rate  of  removal  of  the  residual  fatty 
substances  from  the  catalyzer  to  be  very  slow.  The  fat  clings  strongly 
to  the  catalytic  body.  On  the  contrary  when  the  reaction  is  at  an  end 
the  catalyzer  separates  in  a  flocculent  condition.  Because  of  this, 
Erdmann  is  of  the  opinion  that  the  oxide  and  unsaturated  fat  form 
a  loose  addition  compound  which  is  subsequently  split  by  hydrogen. 
Analysis  of  the  black  nickel  material  obtained  by  extracting  the  fat 
from  used  catalyzer  shows  several  per  cent  of  carbon  to  be  present, 
apparently  united  to  the  nickel  as  a  kind  of  carbide.  The  greater 
portion  of  the  used  catalyzer  consists  of  a  mixture  of  nickel  oxide  and 
suboxide.  The  latter  is  looked  upon  as  Ni20,  described  by  Bellucci 
and  Corelli.*  The  hydrogen  transference  probably  takes  place  in 
one  of  two  ways:  either  an  intermediate  phase  represented  by  the 
compounds 


>0    and 
HC    -Ni/ 


is  formed  (the  latter  compound  carrying  its  hydrogen  very  loosely 
bound)  ;  or  a  decomposition  of  water  may  take  place  in  accordance 
with  the  reaction 

Ni20  +  H20  =  2  NiO  +  H2 

yielding  hydrogen  in  a  nascent  state  which  is  assumed  to  unite  with 
the  unsaturated  fat,  while  the  nickel  oxide  formed  is  reduced  to  the 
suboxide  by  hydrogen  in  the  molecular  condition.  Which  of  these 
views  is  correct  can  be  ascertained  only  by  further  investigations. 
Hydrated  nickel  oxide  or  nickel  carbonate  may  be  used  in  place  of  the 
oxide,  and  under  some  conditions  apparently  also  nickel  salts  such  as 
the  formate  and  acetate.  These  salts  act  as  hydrogen  carriers  only 
after  the  acid  radical  has  been  split  up  and  the  free  metallic  oxide 
formed. 

The  conclusion  is  reached  by  Bedford  and  Erdmann  f  that  some  of 
the  organic  salts  of  nickel  act  like  nickel  oxide  as  catalyzers  and  form 
in  fact  nickel  oxide  by  decomposition  when  heated  in  the  presence  of 
hydrogen.  A  number  of  tests  were  carried  out  using  nickel  formate, 
acetate,  oleate  and  linoleate.  In  one  case  200  grams  of  cottonseed  oil 
were  heated  to  253°  C.  with  nickel  formate  (equivalent  to  2.4  grams 

*  Atti.  R.  Accad.  del  Lincei,  22,  1,  603  and  703. 
t  Jour.  f.  prakt.  Chemie,  1913,  449. 


THE  BASE  METALS  AS  CATALYZERS  81 

NiO),  and  hydrogen  passed  into  the  mixture.  The  oil  quickly  darkened 
due  to  the  formation  of  finely-divided  nickel  and  nickel  oxide.  After 
one  and  one-half  hours  the  solidifying  point  of  the  fatty  product  was 
51.2°  C.  200  grams  of  cottonseed  oil,  6  grams  of  nickel  acetate  and 
20  cc.  of  water  were  heated  and  hydrogen  passed  therethrough.  The 
temperature  was  brought  to  215  to  220  degrees.  The  acetate  retained  its 
green  color  unchanged  and  no  hardening  of  the  oil  was  observed.  The 
temperature  was  then  raised  to  240  to  250  degrees  when  the  mixture 
turned  black  and  in  one  and  one-half  hours  the  solidifying  point  of  the 
hardened  oil  was  49  degrees.  250  cc.  linseed  oil  with  6.3  grams  of 
nickel  linoleate  (equivalent  to  1.2  gram  NiO)  was  treated  with  hydro- 
gen at  2.65  degrees  for  three  hours  yielding  a  product  having  a  solidi- 
fying point  of  44.5°  C.  The  catalyzer  at  the  close  of  the  test  consisted 
of  nickel  oxide  and  suboxide  and  nickel  soap.  Using  11.5  grams  of 
nickel  oleate  to  200  grams  of  cottonseed  oil  it  was  found  that  the  black 
coloration  occurred  above  220  degrees.  Hydrogenation  was  carried  on 
at  250  degrees  and  after  two  hours  the  solidifying  point  was  41  degrees. 
On  the  glass  walls  of  the  reaction  flask  a  brilliant  mirror  of  metallic 
nickel  formed,  which  in  the  course  of  time  separated  in  coarse  flakes. 

A  catalyzer  which  remains  easily  in  suspension  is  prepared  accord- 
ing to  the  Bremen-Besigheimer  Olfabriken  *  by  incorporating  a 
metal  salt  with  an  inorganic  carrier  and  drying  this  product  in  the 
presence  of  the  unsaturated  material  which  is  subsequently  to  be 
hydrogenated,  or  for  that  matter  with  any  suitable  indifferent  liquid. 
The  mixture  is  treated  so  as  to  expel  all  of  the  water  and  a  part  of  the 
volatile  acid  of  the  salt  which  otherwise  might  become  free  and  act 
injuriously  during  the  reduction  process. 

By  this  removal  of  water  and  acid  the  catalyzer  is  put  into  such  a 
condition  that  it  is  capable  of  remaining  suspended  in  oils  and  fats. 
In  the  application  of  the  catalyzer  for  the  reduction  of  the  latter  a 
carrier,  such  as  kieselguhr,  asbestos  and  the  like,  is  treated  with  a 
solution  of  a  metallic  salt,  such,  for  example,  as  nickel  acetate.  After 
drying  the  material  it  is  ground  with  a  quantity  of  oil  so  as  to  yield 
the  catalyzer  in  an  extremely  finely-divided  condition  and  disseminated 
through  the  oil  vehicle.  The  water  and  acetic  acid  are  now  removed 
by  heating  the  mixture  to  150°  to  200°  C.  in  a  closed  vessel  fitted  with 
an  agitator  and  vacuum  pump.  After  the  volatile  material  has  been 
removed  by  such  a  treatment,  hydrogen  is  conducted  through  the 
resulting  product,  f 

*  Zeitsch.  f.  angew.  Chem.  (1913),  Ref.  604. 

t  A  form  of  treatment  of  oil  and  catalyzer  with  hydrogen,  as  disclosed  by  the 
Besigheimer  Olfabriken,  is  noted  in  Seifen.  Ztg.  (1913),  1007. 


82  THE  HYDROGENATION  OF  OILS 

Higgins  *  states  that  the  conversion  of  unsaturated  fatty  acids  or 
their  glycerides  or  other  unsaturated  compounds  into  the  correspond- 
ing saturated  compounds,  by  means  of  hydrogen  in  presence  of  finely- 
divided  nickel  or  other  metal,  is  accelerated  by  the  presence  of  formic 
acid  or  other  volatile  organic  acid.  From  1  to  2  per  cent  of  formic 
acid,  calculated  on  the  weight  of  unsaturated  material,  has  been  found 
a  suitable  proportion.  The  hydrogen  may  be  passed  through  a  vessel 
containing  the  volatile  acid  before  admitting  it  to  the  mixture  of 
unsaturated  compound  and  metal. 

According  to  Wimmer  and  Higgins  f  catalytic  material  may  be 
prepared  from  nickel  salts,  such  as  nickel  formate,  by  mixing  with  a 
protecting  material,  the  latter,  for  example,  being  an  oily  body,  and 
then  reducing  the  salt  to  yield  the  nickel  in  a  metallic  condition.  The 
oil  serves  to  preserve  the  catalytic  properties  of  the  reduced  substance. 

Wimmer  has  observed  that  the  content  of  free  fatty  acid  is  increased 
by  hydrogenation  and  has  offered  as  a  remedy  the  addition  of  drying 
agents  to  the  catalytic  material.  Ignited  sodium  or  magnesium  sulfate 
are  recommended  for  the  purpose.  In  hardening  cottonseed  oil  Wim- 
mer uses  3  to  10  per  cent  of  sodium  sulfate  and  2  to  3  per  cent  of  nickel 
formate  calculated  on  the  weight  of  the  oil.  He  found  a  sample  of 
peanut  oil  containing  0.5  per  cent  of  fatty  acid,  after  hardening  in  this 
manner,  to  contain  0.42  per  cent  of  fatty  acid,  while  without  an  addition 
of  sodium  sulfate  the  acid  content  was  0.72  per  cent.J 

A  flaky  form  of  nickel  catalyzer  is  brought  forward  by  Hagemann 
and  Baskerville  §  to  replace  nickel  supported  on  an  inert  carrier. 
They  observe  that  the  application  of  the  latter  type  of  catalyzers 
involves  a  number  of  technical  difficulties;  for  instance,  on  account 
of  their  finely-divided  state,  such  catalyzers  cannot  be  readily  and 
satisfactorily  separated  and  recovered  from  the  fats,  and,  owing  to 
their  density,  do  not  remain  well  suspended  in  the  oil  treated,  when 
such  suspension  is  desired.  The  use  of  a  metal  precipitated  upon  an 
inert  carrier,  such  as  kieselguhr,  they  note,  has  not  given  entirely 

*  British  Patent  18,282,  Aug.  8,  1912. 

t  French  Patent  454,501,  Feb.  18,  1913.  When  nickel  formate  is  used,  it  serves 
both  as  reducing  agent  and  as  catalyst;  with  zinc  formate,  addition  of  a  known 
catalyst,  such  as  palladium  chloride,  is  desirable.  The  temperature  used  is  pref- 
erably about'  20°  C.  below  that  at  which  the  formate  would  decompose  into  the 
oxalate  at  the  pressure  existing  during  the  operation.  (Higgins,  British  Patent 
23,377,  Oct.  12,  1912.)  Wimmer  and  Higgins  (Seifen.  Ztg.,  1914,  7)  state  that  the 
metal  salts  of  organic  acids  may  be  used  for  the  hydrogenation  of  various  organic 
compounds  of  an  unsaturated  nature  in  addition  to  oils  and  fats. 

J  Seifen.  Ztg.,  1914,  390. 

§  U.  S.  Patent  1,083,930,  Jan.  13,  1914. 


THE  BASE  METALS  AS  CATALYZERS  83 

satisfactory  results,  probably  for  the  reason  that  only  a  small  part 
(one  side)  of  the  film  of  the  precipitated  metal  comes  into  actual  con- 
tact with  the  liquid  to  be  reduced  and  the  hydrogen,  and  the  remainder 
of  the  metal  is  consequently  inactive,  since  the  reacting  materials 
cannot  come  into  contact  therewith.  Other  stated  objections  to  the 
use  of  such  a  catalyst  are  that  the  process  of  revivification  is  quite  an 
expensive  undertaking,  since  the  metal  must  be  dissolved  in  an  acid, 
and  reprecipitated  upon  kieselguhr;  that  it  is  difficult  to  obtain  a 
catalyzer  by  precipitation  and  reduction  methods,  which  is  free  from 
oxides  and  other  impurities;  and  that  fatty  oils  hydrogenated  with 
such  finely-divided  catalyzers  will  contain  metallic  soaps,  such  as 
soaps  having  a  nickel  base,  which  are  undesirable  from  economic 
and  hygienic  standpoints.  Hagemann  and  Baskerville  observe  that 
metals  having  catalytic  activity,  such  as  nickel,  or  cobalt,  brought  into 
a  state  of  extremely  thin  films,  or  flakes,  by  mechanical,  chemical  or 
galvanoplastic  processes,  as,  for  example,  by  the  method  shown  by 
Edison, *  offer  technical  advantages  as  catalysts  in  the  hydrogenation 
of  fatty  oils.  These  films,  or  flakes,  are  obtainable  in  a  state  of  high 
purity,  and  may  be  employed  either  in  the  metallic  (pure)  state  or 
after  being  partially  oxidized.  Films  can  readily  be  prepared,  having 
a  thickness  of  from  one  twenty-thousandth  to  one  forty-thousandth 
of  an  inch,  and  accordingly  the  efficiency  of  a  given  weight  of  a  cata- 
lytic metal,  for  example,  nickel,  when  applied  in  this  form,  is  high, 
owing  to  the  large  amount  of  exposed  surface.  Such  films,  or  flakes, 
will,  on  account  of  their  extreme  thinness,  readily  float  and  remain 
evenly  distributed  throughout  the  whole  mass  of  fats  or  oils.f  The 
separation  of  the  hardened  products  from  the  flaky  nickel,  cobalt,  etc., 
is  said  to  be  accomplished  without  difficulty.  In  the  revivification 
and  recovery  of  the  catalyzer  for  subsequent  use  it  has  been  found 
that  flaky  metals,  as  nickel,  etc.,  admit  of  economical  treatment,  for 
the  flakes  retain  their  physical  form.  In  this  revivification  the  flakes, 
or  films,  from  which  the  fat  has  been  removed  (for  example,  by  ex- 
traction with  a  suitable  solvent)  are  subjected  to  superficial  oxidation 
followed  by  reduction  with  hydrogen  at,  say,  300°  C.,  or  higher,  in  a 
current  of  oxygen  or  air,  or  by  treatment  with  oxidizing  agents  in 
liquids  in  which  the  metallic  flakes  are  suspended.  In  such  a  manner 
Hagemann  and  Baskerville  state  they  can  repeatedly  produce  freshly- 
reduced  surfaces  to  both  sides  of  the  metal  flakes,  or  films,  without 

*  U.  S.  Patent  865,688.     See  also  821,626. 

t  The  author  has  made  use  of  a  form  of  flaky  nickel  derived  from  nickel  carbonyl 
in  hydrogenating  oils  and  has  found  this  form  of  the  metal  to  be  satisfactory  from 
the  catalytic  standpoint. 


84  THE  HYDROGENATION  OF  OILS 

having  recourse  to  conversion  of  the  metal  into  a  soluble  salt,  precipi- 
tating, igniting  and  reducing. 

Another  method*  of  forming  a  catalyzer  involves  the  utilization  of 
the  disintegrating  effect  of  an  electrical  current  or  arc  between  a  pole  or 
poles  of  nickel  immersed  in  a  vehicle  offering  considerable  resistance  to 
the  electric  current,  such  as  water,  or  aqueous  solutions,  thereby  pro- 
ducing nickel  material  in  a  finely-divided  condition,  requiring  little  or 
no  further  treatment  to  serve  as  a  catalyzer.  For  example,  two  elec- 
trodes of  pure  nickel  in  bar  or  rod  form  are  connected  one  to  the  positive 
and  the  other  to  the  negative  pole  of  a  source  of  electricity.  The  ends 
of  the  nickel  rods  are  dipped  in  water  and  brought  in  contact,  then  sep- 
arated so  as  to  form  an  arc  under  the  water.  This  results  in  the  pro- 
duction of  nickel  material  usually  of  a  brown  to  blackish  color  in  a  state 
of  more  or  less  fine  division,  some  of  this  material  often  being  so  fine 
and  flocculent  as  to  remain  suspended  in  water  for  several  days.  Dis- 
tilled water  should  preferably  be  used  though  under  some  circumstances 
saline  solutions  may  be  employed.  By  the  use  of  distilled  water  the  in- 
troduction of  contaminating  bodies  is  practically  or  entirely  avoided. 

Careful  regulation  of  the  arc  is  desirable  in  order  to  avoid  melting 
away  particles  of  nickel  in  the  shape  of  large  fragments  which  are  not 
useful  for  the  present  purpose,  although  some  coarse  material  is  usually 
formed.  When  the  product  contains  such  heavy  nickel  particles  it 
may  be  levigated  and  the  lighter  sludge  separated  from  the  heavy 
nickel  residue.  The  sludge  is  evaporated  to  dryness  when  a  very  light 
nickel  material  is  obtained,  which  may  be  used  at  once  as  a  catalytic 
body  or  may  first  be  reduced  in  hydrogen.  Or,  the  wet  sludge  may  be 
heated  with  oil  to  expel  the  water  in  order  to  produce  a  form  of  nickel 
which  remains  suspended  in  oil  for  a  long  period  and  this  may  be  used 
as  catalytic  basis.  In  such  a  case  it  is  usually  well  to  heat  to  230  to 
250°  C.  in  the  early  stage  of  the  hydrogenation  treatment  and  after  a 
time  the  temperature  may  be  reduced  to  200  degrees  and  lower. 

Boberg  f  prepares  a  catalyst  by  reduction  with  hydrogen  of  a  metal- 
lic compound,  such  as  ignited  nickel  carbonate,  under  such  conditions 
that  the  resulting  product  is  a  complex  compound  of  one  or  more  sub- 
oxides  of  the  metal.  The  preferred  range  of  temperature  during  re- 
duction is  from  230°  to  270°  C.,  the  material  being  heated  for  a  longer 
period  the  lower  the  temperature  employed.  It  is  stated  that  unneces- 
sarily protracted  heating  should  be  avoided  as  leading  to  a  more  com- 
plete reduction  with  loss  of  activity  in  the  product. 

The  product  may  be  collected  for  immediate  use  in  the  medium  in 

*  Ellis,  U.  S.  Patent  1,092;206,  April  7,  1914. 
t  U.  S.  Patent  1,093,377,  April  14,  1914. 


THE  BASE  METALS  AS  CATALYZERS  85 

which  it  is  to  be  used,  e.g.,  oil,  but  if  not  required  at  once  slow  oxidation 
in  the  atmosphere  can  be  allowed,  provided  local  overheating  is  pre- 
vented (which  leads  to  excessive  oxidation)  and  the  material  can  then 
be  kept  without  special  precautions  against  oxidation  and  restored  to 
full  activity  when  required.  For  instance  the  material  may  be  col- 
lected in  water  and  then  filtered  therefrom  and  allowed  to  dry  in  the  air 
or  may  be  collected  in  an  atmosphere  of  hydrogen,  which  is  then  slowly 
replaced  by  oxygen  or  air. 

In  order  to  prepare  it  for  use  the  material  only  requires  to  be  heated 
for  say  one  to  two  hours  at  about  180°  C.  in  an  atmosphere  of  hydrogen 
or  the  catalyst  may  be  treated  with  hydrogen  when  in  suspension  in  a 
suitable  liquid.  When  the  catalyst  is  used  for  hardening  fats  or  oils  no 
special  treatment  of  this  kind  is  necessary  as  the  catalyst  acquires  its 
full  activity  in  the  early  stages  of  the  process. 

The  catalyst  may  be  prepared  by  reducing  to  nickel  as  completely 
as  possible  one  of  the  oxides  of  nickel  and  oxidizing  this  product  with 
air  or  oxygen  diluted  with  an  inert  gas,  the  proportion  of  oxygen  being 
regulated  to  avoid  local  overheating.  This  oxidizing  action  can  be 
carried  out  at  between  300°  and  600°  C. 

Boberg  states  that  he  has  "made  experiments  with  various  prod- 
ucts of  reduction  and  has  obtained  the  following  results:  The  prod- 
uct of  reduction  of  such  a  composition  that  an  ultimate  analysis  gives 
a  proportion  of  nickel  to  oxygen  corresponding  to  an  imaginary  formula 
Ni9.3O,  i.e.,  but  little  suboxide,  produced,  in  a  certain  time,  hardening 
of  a  liquid  fat  up  to  a  melting  point  of  40°  C.,  whereas,  a  product  corre- 
sponding to  an  imaginary  formula  Ni2  esO  gave  in  the  same  time  and 
for  the  same  material  hardening  corresponding  to  a  melting  point  of 
58°  C.  It  appeared,  however,  that  with  a  lesser  proportion  of  nickel  in 
the  product,  i.e.,  a  composition  that  apparently  indicated  the  presence 
of  higher  oxides,  the  product  was  less  active,  while,  at  the  same  time, 
compounds  containing  even  higher  proportions  of  metallic  nickel  than 
that  first  specified  above,  viz.,  Ni9-3O,were  still  less  active  than  the  latter." 

Boron  may  be  used  as  a  catalyzer  according  to  Hildesheimer.*  If 
the  material  is  a  gas  it  is  simply  mixed  with  hydrogen  and  passed  over 
the  boron  material;  if  liquid,  it  is  mixed  with  boron  and  hydrogen  is 
passed  through  it.  When  the  addition  of  hydrogen  is  completed  the 
boron  is  separated  by  filtration  and  is  ready  for  use  again.  The 
catalytic  action  is  assumed  to  depend  upon  the  intermediate  forma- 
tion of  boron  hydride  BH3.  The  rate  of  conversion  is  influenced  by 
the  temperature  and  pressure  as  well  as  the  amount  of  boron.  Cotton- 
seed oil  and  other  unsaturated  compounds,  such,  for  example,  as  ethyl- 
*  Zeitsch.  f.  angew.  Chem.  (1913),  Ref.  583. 


86 


THE  HYDROGENATION  OF  OILS 


ene,  add  hydrogen  under  these  conditions.  In  place  of  boron  some 
of  its  compounds,  such  as  boron  hydride,  and  metallic  compounds  of 
boron,  such  as  aluminium  boride,  may  be  used.  Gases  containing 
hydrogen  may  be  used  in  place  of  pure  hydrogen.* 

On  the  large  scale  the  manufacture  of  catalyzers  by  reduction  of  the 
oxide  of  a  metal  in  a  current  of  hydrogen  has  been  found  to  bring  with 
it  a  train  of  difficulties.  A  method  of  reducing  catalyzer  in  a  con- 
tinuous manner  f  which  simplifies  the  operation  to  a  considerable 
extent  is  shown  in  Fig.  46.  A  charge  of  the  material  to  be  reduced 


FIG.  46. 

is  fed  from  the  hopper  and  feed  arrangement  into  a  series  of  hori- 
zontal parallel  conveyors  1,  2,  3  and  4  into  which  a  current  of  hydrogen 
gas  is  introduced  by  the  pipe  5.  These  conveyors  connect  one  with, 
another  alternately  so  that  the  material  travels  in  one  direction  through 
a  given  conveyor,  then  falls  into  the  conveyor  beneath  and  travels  in 

*  A  process  of  hydrogenation  involving  the  use  of  chloride  of  mercury  is  described 
in  an  Austrian  patent  application  noted  in  Seifen.  Ztg.  (1913),  1413.  According  t,o 
the  method  set  forth  fatty  acids  or  their  glycerides  are  heated  to  a  temperature 
below  180°  C.  with  a  mixture  of  a  difficultly  reducible  inorganic  salt  of  a  base  metal 
in  company  with  chloride  of  mercury  and  at  the  same  time  hydrogen  or  other  reduc- 
ing-gas  mixture  is  passed  through  the  oil. 

t  Ellis,  U.  S.  Patent  1,078,541,  Nov.  11,  1913. 


THE  BASE  METALS  AS  CATALYZERS 


87 


an  opposite  direction.  At  the  same  time  the  material  is  heated  to  the 
proper  temperature  of  reduction  and  throughout  its  travel  is  in  con- 
tact with  a  counter-current  of  hydrogen.  Thus,  the  more  nearly 
reduced  material  is  constantly  progressing  into  a  zone  of  purer  hydro- 
gen, while  the  fresh  raw  material  meets  hydrogen  charged  with  steam. 
In  this  manner  conditions  of  reduction  are  so  facilitated  that  the  use 


FIG.  47. 

of  a  great  excess  of  hydrogen  to  remove  the  steam  does  not  become 
necessary.  After  the  catalyzer  has  been  reduced  it  may  be  mixed 
with  oil  in  another  conveyor  and  be  subsequently  carried  to  a  grinder 
or  beating  apparatus  where  the  coarser  particles  are  broken  down. 

Another  form  of  catalyzer  reducing  chamber  is  shown  in  Fig.  47 
and  consists  of  a  closed  chamber  equipped  with  a  stirrer  and  with  a 
conveyor  to  remove  the  reduced  material.* 

*  Ellis,  U.  S.  Patent  1,084,202,  Jan.  13,  1914. 


CHAPTER  Y 
NICKEL  CARBONYL 

Owing  to  the  interest  manifested  in  nickel  carbonyl  as  a  source  of 
catalytic  nickel  and  because  of  the  difficulties  encountered  in  its  prepa- 
ration the  following  extracts  from  various  publications  on  the  subject 
are  appended. 

The  action  of  carbon  monoxide  on  nickel  was  noted  by  Mond  and 
associates  in  1890.*  When  carbon  monoxide  is  passed  over  finely- 
divided  nickel,  such  as  is  obtained  by  reducing  nickel  oxide  by  hydro- 
gen at  about  400  degrees,  at  a  temperature  between  350  and  450  de- 
grees, carbon  dioxide  is  formed,  and  the  nickel  is  gradually  converted 
into  a  black,  amorphous  powder,  consisting  of  carbon  and  nickel; 
the  composition  of  this  deposit  varies  widely  with  temperature  and 
time.  A  small  quantity  of  nickel  can  thus  change  a  very  large  amount 
of  carbon  monoxide,  the  action  being  complete  and  rapid  at  first,  and 
continuing,  although  at  a  diminishing  rate,  for  several  weeks.  A 
product  containing  as  much  as  85  parts  carbon  to  15  parts  nickel  was 
obtained.  Acids  only  partially  remove  the  nickel;  the  carbon  is  very 
readily  acted  on  by  steam,  carbon  dioxide  and  hydrogen  without  a 
trace  of  carbon  monoxide  being  formed  at  a  temperature  of  350  degrees. 

On  allowing  the  substance  to  cool  in  a  current  of  carbon  monoxide, 
it  was  noticed  that  the  flame  of  a  Bunsen  burner  into  which  the  escap- 
ing gas  was  introduced  became  luminous,  and  when  the  tube  through 
which  the  gas  passed  was  heated,  a  deposit  of  nickel,  mixed  with  a 
small  quantity  of  carbon,  was  obtained.  Mond  and  his  associates 
were  thus  led  to  discover  the  existence  of  a  volatile  nickel  compound. 

To  prepare  this  compound  a  combustion  tube  was  filled  with  nickel 
oxide  and  this  was  reduced  by  hydrogen  at  about  400  degrees;  after 
cooling  the  nickel  to  about  100  degrees,  pure  dry  carbon  monoxide 
was  passed  over  it  without  further  heating,  and  the  issuing  gas  led 
through  a  tube  placed  in  a  freezing  mixture;  the  major  portion  of  the 
nickel  compound  condensed  as  a  colorless  liquid;  but  since  the  gas 
retained  about  5  per  cent,  it  was  collected,  dried  and  again  passed  over 
the  metal.  When  no  more  liquid  condensed,  the  nickel  was  again 

*  Mond,  Langer  and  Quincke,  Proc.  Chem.  Soc.  (1890),  112;  J.  S.  C.  I.  (1890), 
808. 

88 


NICKEL  CARBONYL  89 

heated  to  about  400  degrees  in  a  slow  current  of  pure  carbon  monoxide; 
it  was  then  cooled  to  about  100  degrees,  and  again  submitted  to  the 
action  of  the  gas. 

Nickel  carbonyl  thus  prepared  is  a  colorless  liquid,  which  boils  at 
43  degrees  under  751  mm.  pressure;  its  relative  density  at  17  degrees 
is  1.3185.  It  solidifies  at  —25  degrees  to  a  mass  of  needle-shaped 
crystals.  Its  composition  is  represented  by  the  formula  Ni(CO)4. 
It  dissolves  in  alcohol,  and  more  readily  in  benzene  and  chloroform; 
dilute  acids  and  alkalis  have  no  action  on  it,  but  it  is  oxidized  by  con- 
centrated nitric  acid.  It  reduces  an  ammoniacal  solution  of  cupric 
chloride,  and  also  causes  the  separation  of  silver  from  an  ammoniacal 
solution  of  silver  chloride.  It  interacts  with  chlorine,  forming  nickel 
chloride  and  carbon  oxychloride.  It  is  decomposed  at  180  degrees 
(in  boiling  aniline  vapor)  into  nickel  and  carbon  monoxide.  The 
atomic  weight  of  the  deposited  metal  was  found  in  three  experiments 
to  be  58.52  to  58.64,  a  result  closely  corresponding  with  Russell's 
value,  58.74. 

Numerous  experiments  to  obtain  similar  compounds  with  other  metals,  notably 
with  cobalt,  iron,  copper  and  platinum,  led  to  negative  results.  On  experimenting 
with  specially-purified  cobalt,  in  the  beginning  a  slight  coloration  of  the  Bunsen 
flame  into  which  the  gas  was  led  was  noticed,  but  after  a  time  this  was  no  longer 
observed.  Commercial  cobalt  afforded  a  gas  which  deposited  a  mirror  of  pure 
nickel,  it  being  possible,  in  fact,  to  purify  cobalt  from  nickel  by  carbonic  oxide. 
The  nickel  mirrors  obtained  by  heating  the  carbonic  oxide  compound  do  not  appear 
to  contain  any  trace  of  cobalt. 

Martha  (Chem.  Ztg.  (1891),  915;  J.  S.  C.  I.,  1891,  837)  has  recorded  some  prop- 
erties of  nickel  carbonyl  which  are  of  interest.  He  used  some  impure  ferriferous 
nickel  oxide  as  the  source  of  the  metal.  Under  these  circumstances  the  condensed 
nickel  compound  has  always  a  yellow  tinge,  and  contains  iron,  as  do  also  the  nickel 
films  obtained  by  heating  the  conducting  tube.  The  liquid  after  standing  for  a 
few  hours,  even  in  a  sealed  tube,  deposits  a  brown  compound  containing  iron,  which 
often  explodes  with  great  violence  when  the  liquid  is  poured  off,  the  sides  of  the  tube 
being  simultaneously  covered  with  a  film  of  nickel.  An  apple  green  precipitate 
containing  nickel  is  occasionally  deposited,  together  with  the  brown  iron  compound, 
and  adheres  strongly  to  the  sides  of  the  tube.  The  vapor  of  the  liquid  compound 
exploded  upon  one  occasion  very  violently,  either  owing  to  the  presence  of  a  particle 
of  the  iron  compound  or  to  its  own  explosive  properties. 

Berthelot  *  notes  that  the  vapor  tension  of  nickel  carbonyl  (boiling 
point  46°  C.)  at  16°  C.  is  about  one-fourth  of  an  atmosphere.  A  drop 
of  the  liquid  allowed  to  evaporate  spontaneously  forms  a  certain 
quantity  of  crystals,  which  consist  of  the  solidified  substance,  and 
speedily  volatilize  on  continued  exposure.  It  has  no  sensible  tension 
of  dissociation  at  the  ordinary  temperature,  but  in  contact  with  air 
*  Bull.  Soc.  Chim.  (1892),  13,  431. 


90  THE  HYDROGENATION  OF  OILS 

oxidizes  rapidly.  The  precise  mechanism  of  oxidation  varies  accord- 
ing to  the  conditions  under  which  it  takes  place.  For  example,  when 
an  inert  gas,  charged  with  the  vapor  of  nickel  carbonyl,  is  passed 
through  a  strongly  heated  tube,  the  products  are  metallic  nickel  and 
carbon  monoxide,  as  observed  by  Mond  and  his  colleagues.  These 
investigators  also  found  when  nickel  carbonyl  is  heated  sharply  to 
70°  C.,  at  which  point  detonation  takes  place,  that  the  same  bodies 
are  formed. 

Berthelot,  however,  has  observed  that  a  certain  amount  of  carbon  dioxide  and 
carbon  is  produced.  He  is  of  the  opinion  that  this  reaction  determines  the  occur- 
rence of  the  detonation,  as  the  equation 

2  CO  =  CO2  +  C 

implies  the  evolution  of  38.8  calories,  i.e.,  77.6  calories  for  the  4  mols.  of  carbon 
monoxide  in  Ni(CO)4.  The  only  assumption  necessary  to  justify  this  view  is  that 
the  heat  of  combination  of  Ni  and  CO  is  less  than  77.6  calories. 

The  reactions  of  nickel  carbonyl  are  generally  those  dependent  upon 
the  presence  in  it  of  nickel,  but  when  they  are  induced  gently  and  at 
low  temperature,  bodies  comparable  to  organo-metallic  compounds 
are  formed.  The  vapor  of  nickel  carbonyl  is  not  sensibly  soluble  in 
water  or  dilute  acid  or  alkaline  solutions  or  cuprous  chloride.  Hydro- 
carbons are  its  natural  solvents;  spirits  of  turpentine  is  specially 
suitable,  and  can  be  used  for  determining  it.  Explosion  of  a  mixture 
of  nickel  carbonyl  and  oxygen  can  be  effected  by  violent  agitation  over 
mercury  as  well  as  by  direct  ignition.  Slow  union  takes  place  when 
such  a  mixture  is  kept  in  contact  with  a  little  water.  In  contact  with 
strong  sulfuric  acid  dry  liquid  nickel  carbonyl  explodes  after  a  short 
interval,  but  if  in  the  form  of  vapor  and  diluted  with  nitrogen  it  is 
decomposed  gradually,  the  theoretical  quantity  of  carbon  monoxide 
being  liberated.  Strong  caustic  potash  has  no  perceptible  action  on 
nickel  carbonyl.  Gaseous  ammonia  does  not  act  immediately  per  se, 
but  if  a  little  oxygen  be  added,  fumes  are  produced,  and  if  the  action 
of  oxygen  be  continued  a  whitish  deposit  of  complex  composition  is 
gradually  formed  which  is  destroyed  with  charring  on  being  heated. 

Sulfuretted  hydrogen  acts  on  nickel  carbonyl  vapor,  mixed  with 
nitrogen  in  the  cold,  a  black  sulfide  (of  nickel)  being  precipitated. 
Phosphoretted  hydrogen  under  similar  conditions  gives  a  brilliant 
black  deposit.  Nitric  oxide  if  mixed  with  nickel  carbonyl  vapor, 
diluted  with  nitrogen,  or  passed  into  the  liquid  itself,  produces  blue 
fumes,  which  fill  the  whole  vessel.  The  formation  of  nickel  carbonyl 
proves  carbon  monoxide  to  be  capable  of  forming  organo-metallic 
compounds  similar  to  those  derived  from  hydrocarbons,  and  analogous 
to  the  salts  of  rhodizonic  and  croconic  acids  produced  by  the  union  of 


NICKEL  CARBONYL  91 

the  condensed  derivatives  of  carbon  monoxide  with  an  alkaline  metal. 
Nickel  carbonyl  serves  as  an  example  of  the  tendency  of  carbon  mon- 
oxide to  form  loose  combinations  and  products  of  condensation,  in 
virtue  of  its  character  as  an  unsaturated  body. 

Nickel  carbonyl,  according  to  Berthelot,*  can  be  preserved  under 
water,  but  if  contained  in  a  bottle  with  an  ordinary  ground-in  stopper 
becomes  slowly  oxidized,  and  a  layer  of  apple  green  nickel  hydrate  is 
formed,  which  is  free  from  carbon.  A  portion  of  it,  however,  makes  its 
way  out  of  the  bottle  and  is  oxidized,  forming  a  fume  which  is  deposited 
on  adjacent  objects. 

In  order  to  examine  the  product  of  oxidation  Berthelot  kept  a  bottle  of  nickel 
carbonyl  in  a  double  casing  of  tin  plate  and  succeeded  in  collecting  a  few  decigrams 
of  a  complex  oxide,  which  appeared  white  in  small  quantity,  but  had  a  greenish 
tinge  when  viewed  in  mass.  It  was  found  to  be  the  hydrated  oxide  of  an  organo- 
metallic  compound  of  nickel,  and  upon  analysis  gave  figures  corresponding  to  the 
formula  C2OjNis  •  10  H^O.  It  therefore  appears  to  be  the  oxide  of  a  complex  radical 
analogous  to  croconic  and  rhodizonic  acids. 

The  fact  that  under  ordinary  circumstances  nickel  alone  is  acted  on  when  a 
mixture  of  this  metal  with  any  other  metallic  or  mineral  substance  is  treated  by 
carbonic  oxide  gas,  led  Mond  (J.  S.  C.  I.,  1891,  836)  to  institute  experiments  to 
ascertain  whether  it  would  not  be  possible  by  means  of  carbonic  oxide  to  extract 
nickel  direct  from  its  ores,  and  such  metallurgical  products  as  nickel  speiss  and  nickel 
matte.  As  the  nickel  is  volatilized  at  the  ordinary  temperature  in  the  form  of  a 
vapor  disseminated  through  other  gases  from  which  it  can  be  deposited  without 
first  condensing  the  nickel  compound,  by  simply  heating  these  gases  to  the  moderate 
temperature  of  200°  C.,  as  it  is  thus  obtained  in  the  form  of  bright  coherent  masses 
of  great  purity,  as  the  carbonic  oxide  used  is  completely  liberated  and  can  be  em- 
ployed over  and  over  again,  and  as  small  quantities  of  the  poisonous  nickel  com- 
pound which  may  escape  decomposition  would  thus  never  leave  the  closed  apparatus 
in  which  the  process  would  be  carried  out,  it  seemed  probable  that  such  a  process 
might  be  capable  of  industrial  application,  and  might  prove  more  economical  than 
the  complicated  operations  metallurgists  have  to  resort  to  to  produce  tolerably  pure 
nickel. 

Experiments  carried  out  in  conjunction  with  Langer,  with  a  great  variety  of 
nickel  ores  from  all  parts  of  the  world,  containing  from  4  to  40  per  cent  of  nickel, 
as  well  as  a  number  of  samples  of  nickel  speiss  and  nickel  matte,  proved  that  as 
long  as  the  nickel  is  combined  with  arsenic  or  sulfur  the  process  was  successful. 
In  the  majority  of  cases  Mond  was  able  to  extract  the  nickel  almost  completely  in 
three  or  four  days.  Such  ores  or  matte  or  speiss  have  in  the  first  instance  to  be 
calcined,  so  as  to  convert  the  nickel  completely  into  oxide.  The  mass  is  then  reduced 
in  a  current  of  hydrogen-containing  gases  —  in  practice  water  gas  at  a  temperature 
of  450°  C.  It  is  cooled  down  to  ordinary  temperature  and  treated  with  any  good 
apparatus  for  treating  solids  by  gases.  Methodical  apparatus  moving  the  reduced 
ore  in  opposite  directions  to  the  current  of  carbon  monoxide,  at  the  same  time  exposing 
fresh  surfaces,  facilitate  the  operation.  After  a  certain  time  the  action  of  the  car- 
bon monoxide  upon  the  nickel  becomes  sluggish.  The  mass  is  then  heated  to  about 

*  Bull.  Soc.  Chim.  (1892),  434. 


92  THE  HYDROGENATION  OF  OILS 

350°  C.  in  a  current  of  carbon  monoxide,  which  regenerates  the  activity  of  the  nickel. 
This  may  be  done  in  the  same  apparatus,  but  it  is  preferable  to  use  a  separate  appa- 
ratus connected  with  the  first,  and  from  which  the  material  is  returned  to  the  first 
by  mechanical  means,  so  that  each  apparatus  can  be  kept  at  the  same  temperature. 
The  carbon  monoxide  gas  can  be  employed  dilute,  as  it  is  obtained  from  gas  pro- 
ducers; but  since  it  is  continuously  recovered,  a  purer  gas,  such  as  can  be  cheaply 
prepared  by  passing  carbon  dioxide  through  incandescent  coke,  is  more  advanta- 
geous, as  it  extracts  the  nickel  more  quickly  and  requires  smaller  apparatus.  The 
gas  charged  with  the  nickel  compound  leaving  the  apparatus  is  passed  through  tubes 
or  chambers  heated  to  about  200°  C.,  in  which  the  nickel  is  deposited.  The  gas 
leaving  these  tubes  is  returned  to  the  first  apparatus,  and  circulates  continuously. 
From  time  to  time  the  nickel  is  removed  from  the  tubes  in  which  it  has  been 
deposited.  To  facilitate  this  operation  thin  nickel  sheets,  bent  to  fit  the  tubes, 
are  inserted,  on  which  the  nickel  deposits,  and  which  are  easily  taken  out.  The 
metal  so  obtained  is  almost  chemically  pure;  only  very  rarely  in  the  case  of  certain 
ores  it  is  slightly  contaminated  with  iron.  As  the  nickel  is  deposited  in  perfectly 
coherent  films  upon  heated  surfaces  exposed  to  the  gas  containing  the  nickel  car- 
bonyl,  it  was  found  possible  to  produce  direct  from  such  gas,  articles  of  solid  nickel 
or  goods  plated  with  nickel.  This  result  can  also  be  obtained  by  immersing  heated 
articles  in  a  solution  of  nickel  carbonyl  in  such  solvents  as  benzole,  petroleum,  tar  oils, 
etc.,  or  by  applying  such  solution  to  the  heated  articles  with  a  brush  or  otherwise. 

Mond  *  observes  that  a  mixture  of  the  vapor  and  air  explodes  readily 
but  not  very  violently.  The  pure  liquid  does  not  explode,  but  at  high 
temperatures  it  decomposes.  The  vapor  has  a  characteristic  odor 
and  is  poisonous.  It  produces  an  extraordinary  reduction  of  tempera- 
ture when  injected  subcutaneously,  sometimes  as  much  as  12  degrees. 
The  liquid  can  be  distilled,  but  not  from  solution  in  liquids  of  a  higher 
boiling  point  as  decomposition  then  occurs,  finely-divided  nickel  being 
separated  and  carbonic  oxide  being  evolved. 

When  attacked  by  oxidizing  agents,  e.g.,  nitric  acid,  chlorine,  or  bromine  or  by 
sulfur,  decomposition  ensues,  nickel  salts  being  formed  and  carbon  dioxide  liber- 
ated. Metals,  alkalies,  non-oxidizing  acids  and  the  salts  of  other  metals  produce  no 
change.  Nickel  carbonates  of  composition  varying  with  the  hygroscopic  state  of 
the  atmosphere  are  formed  by  exposing  the  liquid  to  the  action  of  the  air.  These 
precipitates  dissolve  easily  in  dilute  acid.  An  intense  blue  coloration  is  obtained 
when  nitric  oxide  is  passed  through  a  solution  of  nickel  carbonyl  in  alcohol  (Berthelot). 

Nickel  carbonyl  is  very  diamagnetic,  and  an  almost  perfect  non-conductor  of 
electricity  (Quincke).  All  other  nickel  compounds  are  paramagnetic.  It  is  opaque 
for  rays  beyond  the  wave  length  3820,  and  its  flame  gives  a  continuous  spectrum 
(Liveing  and  Dewar). 

Perkin  found  the  power  of  magnetic  rotation  of  nickel  carbonyl  to  be  greater 
than  that  of  any  other  substance  he  has  examined,  except  phosphorus.  Mond  and 
Nasini  found  the  atomic  refraction  to  be  about  2.5  times  as  large  as  in  any  other 
nickel  compound,  and  the  former  proved  it  to  have  great  refractive  and  dispersive 
powers.  The  atomic  refraction  of  a  liquid  ferro-carbonyl  bears  about  the  same 

*  J.  S.  C.  I.,  1892,  750. 


NICKEL  CARBONYL 


93 


ratio  to  the  atomic  refraction  of  other  iron  compounds.  This  ferro-carbonyl  is 
similar  in  preparation  and  properties  to  the  nickel  carbonyl,  and  at  180°  C.  the  iron 
is  thrown  down  in  bright  mirror-like  form,  carbon  monoxide  being  liberated.  Its 
composition  is  Fe(CO)6. 

To  extract  nickel  from  its  ores  Mond  used  an  apparatus,  Fig.  48, 
consisting  of  a  cylinder  divided  into  many  compartments,  through 
which  the  properly  prepared  ore  is  passed  very  slowly  by  means  of 
stirrers  attached  to  a  shaft.  On  leaving  the  bottom  of  this  cylinder 
the  ore  passes  through  a  transporting  screw,  and  from  this  to  an 
elevator  which  returns  it  to  the  top  of  the  cylinder,  so  that  it  passes 
many  times  through  the  cylinder  until  all  the  nickel  is  volatilized. 
Into  the  bottom  of  this  cylinder  carbonic  oxide  is  passed,  which  being 
charged  with  nickel  carbonyl  vapor  leaves  at  the  top,  and  passes 
through  the  conduits  shown  into  tubes  set  in  a  furnace,  and  heated 
to  200°  C.  Here  the  nickel  separates  from  the  nickel  carbonyl.  The 
carbonic  oxide  is  regenerated  and  taken  back  to  the  cylinder  by  means 
of  a  fan,  so  that  the  same  gas  is  made  to  carry  fresh  quantities  of  nickel 
out  of  the  ore  in  the  cylinder,  and  to  deposit  it  in  the  tubes  an  infinite 
number  of  times.  When  the  carbonic  oxide  comes  out  at  the  top  of 


the  cylinder  it  passes  through  a  filter  to  catch  any  dust  it  may  contain. 
The  carbonic  oxide,  on  escaping  from  the  depositing  tubes,  is  passed 
through  another  filter,  thence  through  a  lime  purifier  to  absorb  any 
carbon  dioxide  which  may  have  been  formed.  By  means  of  this 
apparatus  nickel  has  been  extracted  from  a  great  number  of  ores,  in 
times  varying,  according  to  the  nature  of  the  ores,  from  a  few  hours  to 
several  days. 

A  review  by  Mond  of  his  experimental  work  on  nickel  carbonyl  * 
is  instructive. 

*    J.  S.  C.  I.,  1895,  945. 


94  THE  HYDROGENATION  OF  OILS 

Mond  stated  that  "in  the  course  of  these  experiments  finely-divided  nickel, 
formed  by  reducing  nickel  oxide  at  400°  C.  by  hydrogen,  was  treated  with  pure  CO 
in  a  glass  tube,  at  varying  temperatures,  for  a  number  of  days,  and  was  then  cooled 
down  in  a  current  of  CO  before  it  was  removed  from  the  tube.  In  order  to  keep 
the  poisonous  CO  out  of  the  atmosphere  of  the  laboratory,  we  simply  lit  the  gas 
escaping  from  the  apparatus.  To  our  surprise  we  found  that,  while  the  apparatus 
was  cooling  down,  the  flame  of  the  escaping  gas  became  luminous  and  increased  in 
luminosity  as  the  temperature  got  below  100°  C.  On  a  cold  plate  of  porcelain  put 
into  this  luminous  flame,  metallic  spots  were  deposited  similar  to  the  spots  of  arsenic 
obtained  with  a  Marsh  apparatus;  and  on  heating  the  tube  through  which  the  gas 
was  escaping  we  obtained  a  metallic  mirror,  while  the  luminosity  disappeared." 

"At  the  first  moment  we  thought  that  there  must  be  an  unknown  element  in  our 
nickel  giving  rise  to  the  production  of  this  effect,  but  when  we  examined  the  mirrors 
we  found  them  to  consist  of  pure  nickel.  As  it  seemed  so  very  improbable  that  so 
heavy  a  metal  as  nickel  should  form  a  readily  volatile  compound  with  CO,  we  puri- 
fied our  CO  as  perfectly  as  possible  but  still  obtained  the  same  results." 

"We  now  endeavored  to  isolate  this  curious  and  interesting  substance  by  prepar- 
ing the  nickel  with  great  care  at  the  lowest  possible  temperature,  and  treating  this 
nickel  with  CO  at  about  50°  C.,  and  thus  we  gradually  increased  the  amount  of  the 
volatile  nickel  compound  in  the  gases  passing  through  the  apparatus.  We  absorbed 
the  excess  of  CO  by  cuprous  chloride  solution,  and  thus  obtained  a  residue  of  several 
cubic  centimeters,  containing  the  volatile  nickel  compound  mixed  with  a  little 
nitrogen.  By  passing  this  gas  through  a  heated  tube  we  separated  the  nickel,  obtain- 
ing an  increased  volume  of  gas,  and  found  in  this  a  quantity  of  CO  corresponding  to 
about  four  equivalents  for  one  equivalent  of  nickel.  By  further  improving  our 
method  of  preparing  the  finely-divided  nickel  and  by  passing  the  resulting  gas 
through  a  refrigerator,  cooled  by  snow  and  salt,  we  at  last  succeeded  in  liquefying 
this  compound,  and  were  able  to  produce  it  with  ease  and  facility  in  any  quantity 
we  desired."  Nickel  carbonyl  "is  soluble  in  alcohol,  petroleum  and  chloroform; 
it  is  not  acted  upon  by  dilute  acids  or  alkalies,  and  can  be  readily  distilled  without 
decomposition.  But  on  heating  the  gas  to  150°  C.,  it  is  completely  dissociated  into 
its  components,  pure  CO  being  obtained  and  the  nickel  being  deposited  in  a  dense 
metallic  film  upon  the  sides  of  the  vessel  in  which  it  is  heated. " 

"  For  a  long  time,  while  we  were  engaged  in  investigating  the  physical  and  chem- 
ical properties  of  this  interesting  substance  —  which  was  without  parallel  in  the 
history  of  chemistry  —  and  while  we  were  endeavoring  to  obtain  other  similar  com- 
pounds with  other  metals,  I  had  myself  no  suspicion  that  this  substance,  which  was 
until  then  only  obtainable  by  very  careful  and  elaborate  laboratory  manipulations, 
should  ever  become  available  for  industrial  purposes.  But  the  longer  we  went  on 
preparing  it  for  our  investigations,  the  more  easy  we  found  it  to  prepare  it  in  quan- 
tity, after  we  once  knew  exactly  the  best  conditions  for  so  doing.  After  that  I 
came  to  the  conclusion  that  it  ought  to  be  possible  to  make  use  of  the  ease  with 
which  nickel  is  converted  into  a  volatile  gas  by  CO,  while  practically  all  other  metals, 
and  notably  cobalt  (which  is  so  difficult  to  separate  from  nickel  by  other  methods), 
was  not  acted  upon  by  this  gas,  for  separating  nickel  from  cobalt  and  other  metals 
on  a  manufacturing  scale,  and  for  obtaining  it  in  a  very  pure  state." 

"I  erected  a  plant  on  a  large  scale  near  Birmingham,  and  after  several  years  of 
hard  work,  during  which  the  apparatus  has  had  to  be  several  times  reconstructed 
so  as  to  fulfil  all  the  conditions  of  this  rather  delicate  process,  we  have  succeeded 
in  our  object,  and  now  have  for  some  time  produced  nickel  at  the  rate  of  a  ton  and 


NICKEL  CARBONYL  95 

a  half  per  week  from  the  Canadian  nickel  copper  matte  imported  into  England. 
This  matte,  which  contains  about  40  per  cent  of  nickel,  and  an  equal  quantity  of 
copper,  is  carefully  roasted  to  drive  out  the  sulfur  as  far  as  possible,  and  is  then 
subjected  to  the  action  of  hydrogenous  gases,  either  water  gas  or  producer  gas,  rich 
in  hydrogen,  in  an  apparatus  which  is  called  the  'reducer,'  the  temperature  of 
which  is  under  perfect  control,  so  that  400°  C.  is  never  exceeded.  From  this  appar- 
atus the  substance,  which  is  now  reduced  to  the  metallic  state,  is  taken  through  air- 
tight conveyors  and  elevators  into  another  apparatus  called  the  '  volatilizer, '  in 
which  it  is  subjected,  at  a  temperature  not  exceeding  80°  C.,  to  the  action  of  CO 
gas." 

"This  apparatus  consists  of  an  iron  cylinder,  divided  into  numerous  compart- 
ments by  shelves,  and  provided  with  a  stirring  device,  which  gradually  moves  the 
material  from  the  top  to  the  bottom,  while  the  CO  gas  passes  through  in  an  opposite 
direction.  The  CO  gas,  which  should  be  as  rich  as  practicable,  we  prepare  by  pass- 
ing pure  CO2  through  incandescent  coke;  the  pure  CO2  we  make  by  passing  the  flue 
gas  of  a  boiler  or  of  a  fire  through  a  solution  of  carbonate  of  potash,  and  subsequently 
boiling  the  solution.  The  CO  gas,  charged  with  nickel  carbonyl,  leaving  the  volatil- 
izer, is  passed  through  a  series  of  tubes  or  chambers,  heated  to  about  180°  C.,  in 
which  the  nickel  is  deposited  in  various  forms,  according  to  the  speed  of  the  gas 
current,  the  richness  of  the  gas  and  the  existing  temperature.  The  CO  gas,  thus 
almost  completely  freed  from  the  nickel,  is  taken  back  by  means  of  a  blower  into 
the  volatilizer,  where  it  takes  up  a  fresh  quantity  of  nickel  and  is  constantly  used 
over  and  over,  so  that  the  quantity  consumed  is  limited  to  the  very  small  amount 
of  unavoidable  loss  through  leakage  of  the  plant." 

"The  material  under  treatment  is  repeatedly  taken  from  the  volatilizer  to  the 
reducer  and  vice  versa,  by  means  of  air-tight  conveyors  and  elevators,  until  the 
amount  of  nickel  volatilized  begins  to  fall  off.  It  is  then  roasted  again  to  remove 
the  sulfur  which  it  still  contains,  and  is  treated  by  sulfuric  acid  to  dissolve  part  of 
the  copper.  The  residue,  containing  nickel,  some  copper  and  the  other  impurities 
of  the  matter  is  again  subjected  to  the  previously  described  treatment  until  the 
nickel  has  been  extracted  as  far  as  practicable;  and  the  ultimate  residue,  still  con- 
taining a  few  per  cent  of  nickel,  is  melted  up  into  matte  again." 

Nickel  carbonyl  is  decomposed  *  by  passage  through  a  mass  of  pel- 
lets of  metallic  nickel,  heated  to  about  200°  C.,  causing  nickel  to  be 
deposited  and  the  pellets  to  increase  in  size.  The  apparatus  con- 
sists of  a  vertical  cylinder,  in  which  the  pellets  are  placed,  with  heat- 
ing spaces  formed  by  an  outer  casing.  A  vertical,  cooled,  perforated 
tube  for  the  gaseous  carbonyl  leads  from  the  top  down  the  center  of 
the  mass  of  pellets,  nearly  to  the  bottom  of  the  cylinder.  To  prevent 
the  pellets  cohering,  they  are  kept  in  motion  by  continuously  with- 
drawing them  from  the  lower  end,  mechanically  screening  them  with 
the  assistance  of  worm  conveyors,  and  returning  the  small  ones  by  an 
elevator  to  a  feeding  hole  at  the  upper  end  for  further  treatment  with 
the  carbonyl.  The  pellets  which  have  sufficiently  increased  in  size 
are  passed  from  the  screen  and  thence  through  a  valved  opening  into 
a  collecting  chamber. 

*  Mond,  British  Patent  1106,  Jan.  14,  1898. 


96  THE  HYDROGENATION  OF  OILS 

In  extracting  nickel  by  means  of  carbon  monoxide  from  mixtures 
of  nickel  and  other  metals,  obtained  by  reducing  the  mixed  oxide  with 
gas  containing  carbon  monoxide,  Fierz  *  displaces  the  carbon  monoxide 
by  hydrogen  or  removes  it  by  suction  from  the  presence  of  the  re- 
duced metals  while  the  temperature  is  maintained  above  that  at  which 
nickel  will  decompose,  or  combine  with,  carbon  monoxide.  The 
temperature  is  then  reduced  to  that  required  for  the  formation  of 
nickel  carbonyl  and  the  gas  readmitted. 

Longer  f  describes  an  apparatus  for  obtaining  nickel  from  nickel 
carbonyl.  Vessels  containing  the  nickel  carbonyl  are  heated  by ,  a 
number  of  gas  flames,  each  of  which  is  situated  in  a  chamber  formed 
by  ribs  on  the  vessel  and  an  outer  casing;  the  liberated  gases  pass  away 
by  an  escape  pipe,  which  is  surrounded  by  an  annular  cooling  chamber. { 

James  Dewar  §  remarks  that  the  nickel  carbonyl  vapor  at  ordinary 
pressures  is  very  unstable,  its  components  becoming  rapidly  disso- 
ciated with  explosion  on  moderate  elevation  of  temperature,  so  that 
its  production  has  hitherto  been  carried  on  at  a  moderately  low  tem- 
perature, such  as  50°  C.  Dewar  has  found  that  under  considerable 
pressure,  ranging  from  2  atmospheres  to  100  atmospheres,  the  com- 
pound, either  as  vapor  or  as  liquid,  is  much  more  stable,  and  there- 
fore higher  temperatures  can  be  used  in  its  production,  whereby  the 
rapidity  of  process  of  manufacture  is  greatly  increased.  Thus  for  the 
gasification  of  the  nickel  a  temperature  of  100°  C.  with  a  pressure  of 
15  atmospheres  is  suitable,  or  a  temperature  of  180°  C.  with  a  pres- 
sure of  80  atmospheres.  The  spongy  nickel  obtained  by  the  reduction 
by  means  of  water  gas,  if  treated  at  the  temperature  and  pressure 
mentioned,  combines  rapidly  with  the  carbonic  oxide,  producing  vapor 
of  nickel  carbonyl.  This  vapor,  with  the  excess  of  carbonic  oxide  in 
which  it  is  diffused  while  still  under  pressure,  on  being  passed  through 
tubes  of  a  higher  temperature,  becomes  dissociated  depositing  metallic 
nickel.  || 

In  the  author's  laboratory  nickel  carbonyl  has  been  extensively 
examined  and  has  proved  a  satisfactory  source  of  nickel  catalyzer. 
The  carbonyl  readily  decomposes  at  temperatures  between  125°  and 
180°  C.  and  when  decomposed  in  the  presence  of  oil  under  some  con- 
ditions the  resulting  nickel  is  very  finely  divided  and  imparts  to  the 

*  British  Patent  4249,  Feb.  19,  1913. 
t  British  Patent  13,350,  June  28,  1905. 

|  See  also  U.  S.  Patent  815,717,  Mar.  20,  1906;  825,844,  July  10,  1906;  and 
865,969,  Sept.  10,  1907. 

§  U.  S.  Patent  760,852,  May  24,  1904. 

II  Electrochem.  and  Met.  Ind.  (1904),  291. 


NICKEL  CARBONYL  97 

oil  an  inky  black  color.  Even  after  standing  for  days  or  even  weeks 
the  nickel  remains  in  suspension.  A  sample  of  cottonseed  oil  carrying 
about  one-half  of  one  per  cent  of  nickel  precipitated  from  nickel  car- 
bonyl  was  exposed  to  the  action  of  a  current  of  hydrogen  gas  under 
practically  atmospheric  pressure  for  a  period  of  one  hour  and  a  solid 
product  resulted  having  a  melting  point  of  47.6°  C.  and  a  refractive 
index  of  1.4445. 


FIG.  49.  —  Photo-micrograph  of  Nickel  Catalyzer  derived  from 
Nickel  Carbonyl.     X  100. 

The  greatest  difficulty  in  the  use  of  nickel  carbonyl  appears  to  be 
the  removal  of  finer  portions  of  the  nickel  precipitate  from  the  oil 
after  hydrogenation,  but  this  may  be  accomplished  by  the  observance 
of  due  precaution  in  filtration.  The  used  catalyzer  recovered  by  filtra- 
tion is  still  active  and  may  be  used  until  its  catalytic  properties  are 
spent.  The  spent  material  may  be  regenerated  more  easily  than  is 
the  case  with  catalyzers  consisting  of  nickel  supported  on  a  voluminous 
carrier  of  inert  material.* 

*  Apparatus  adapted  for  handling  nickel  carbonyl  and  hydrogenating  oils  with 
the  nickel  material  obtained  by  its  decomposition  is  shown  in  U.  S.  Patent  to  Ellis, 
1,095,144,  Apr.  28,  1914. 


CHAPTER   VI 
THE  RARE   METALS  AS   CATALYZERS 

As  a  catalyzer  in  this  field  palladium  has  received  considerable 
study,  for,  in  spite  of  high  first  cost,  its  pronounced  effectiveness, 
together  with  its  ability  to  effect  hydrogenation  at  relatively  low 
temperatures,  makes  it  particularly  attractive. 

Many  years  ago,  Fokin  *  stated  that  he  regarded  palladium  as  the 
most  powerful  of  all  catalyzers,  having  found  that  reduction  takes 
place  readily  at  80°  to  90°  C.,  while  with  nickel,  a  temperature  of  180° 
to  200°  C.  was  necessary  for  practical  hydrogenation.  Fokin's  experi- 
ments at  that  time  were  concerned  with  electrolytic  reduction.  By 
this  means  he  reduced  linseed,  wood,  castor  and  cod  liver  oil.  He 
found  that  while  palladium  black  would  reduce  oleic  acid  completely 
to  stearic  acid,  platinum  black  under  the  same  conditions  gave  only 
24  per  cent  of  stearic  acid. 

Paal  f  worked  with  colloidal  palladium  preparations  and  hydro- 
genated  castor,  olive,  fish  oil  and  animal  fats.  He  found  that  sesame 
oil,  after  hydrogenation,  showed  the  Baudoin  reaction  only  very 
faintly,  while  cottonseed  oil  no  longer  responded  to  the  Becchi  and 
Halphen  reaction.  Skita  has  worked  with  palladium  incorporated 
with  a  protective  colloid. 

Paal  recommends  t  platinum  or  palladium  chloride  admixed  with  a 
neutralizing  agent  such  as  sodium  carbonate.  He  states  that  the 
reduction  of  fats  and  unsaturated  fatty  acids  of  animal  and  vegetable 
origin  may  be  effected  by  allowing  hydrogen  to  act  on  these,  in  presence 
of  platinum  metals,  or  protohydroxide  compounds  of  the  latter,  which 
have  been  deposited  upon  certain  finely-divided  substances  and  act  as 
catalyzers  or  carriers  of  hydrogen.  It  has  also  been  ascertained  that 
the  reduction  of  the  fats  and  fatty  acids  may  be  effected  by  hydrogen 
in  presence  of  solid  salts  of  the  platinum  metals.  Both  the  simple 
salts,  such  as  palladium  protochloride  (PdCk),  platinum  protochloride 
(PtCl2),  platinum  chloride  (PtCl4),  platinum  hydrochloride  (H2PtCl6), 
platinum  sulfate  and  the  double  salts,  for  instance  potassium 

*  Chem.  Ztg.  [2],  1906,  758;  [1],  1907,  324. 
t  Ber.,  41,  2282. 

t  U.  S.  Patent  1,023,753,  April  16,  1912. 
98 


THE  RARE  METALS  AS  CATALYZERS         99 

chloroplatinate  (K^PtCle),  copper  platinochloride,  may  be  used. 
When  the  double  salts  are  used,  care  must  be  taken  that  no  anticata- 
lytic  substances,  such  for  instance  as  lead,  find  their  way  into  the 
reduction  mixture.  Use  may  be  made  of  salts  whose  acid  radicals  or 
other  constituents  are  themselves  reduced  by  hydrogen,  for  example 
acid  platinous  oxalate.  In  all  cases  the  method  is  simple;  and  it  is 
distinguished  from  those  in  which  the  finely-divided  metals  are  used 
by  the  omission  of  the  preparation  of  the  finely-divided  platinum 
metals  or  their  protohydroxides  and  of  the  deposition  on  special 
carriers. 

The  salts  in  a  crushed  condition,  preferably  in  the  state  of  powder,  are  mixed 
with  the  fats  or  fatty  acids  to  be  hydrogenated;  and  hydrogen  is  allowed  to  act  on 
this  mixture,  with  stirring,  at  temperatures  below  100  degrees  preferably  under  a 
pressure  of  several  atmospheres.  In  a  short  time  the  solid  reduction  product  of  the 
fat  or  fatty  acid  will  be  obtained.  All  that  is  necessary  to  insure  the  action  of  the 
solid  salts  of  the  platinum  metals  is  that  they  must  be  present  in  the  solid  form 
during  the  progress  of  the  reaction.  The  salts  may  also  be  added  to  the  fats  in  a 
dissolved  condition  (for  example  in  aqueous  solution),  the  solvent  being  evaporated 
before  or  at  the  beginning  of  the  reduction  process.  A  suspension  of  the  solid  salts 
may  also  be  used.  For  example,  the  salts  of  the  platinum  metals  may  be  triturated 
with  a  portion  of  the  fat  or  oil  that  is  to  be  reduced,  the  mixture  being  then  added 
to  the  main  portion  of  the  fats  or  fatty  acids  to  be  reduced.  Or  a  suspension  of 
the  salts  in  mineral  oil  may  be  prepared,  and  this  mixture  may  be  added  to  the  sub- 
stances that  are  to  be  reduced,  in  which  case  the  suspensory  medium  may  be  elimi- 
nated during  the  process  of  reduction.  A  single  salt  of  a  platinum  metal  may  be 
used,  or  several  salts,  and  even  several  platinum  metals  may  be  mixed  together; 
and  the  salts  may  also  be  used  in  conjunction  with  the  platinum  metals  which  have 
been  deposited  on  carriers,  devoid  of  anticatalytic  action,  such  as  copper,  or  mag- 
nesium carbonate.  It  is  probable  that,  during  the  process,  the  salts  of  the  platinum 
metals  are  split  up  into  metal  and  free  acid,  for  example: 

PdCl2  +  H2  =  Pd  +  2  HC1. 

In  any  case,  however,  the  solid  platinum  metal  salts  greatly  facilitate  the  absorp- 
tion of  hydrogen  by  fats  and  fatty  acids.  Very  small  quantities  of  the  platinum- 
metal  salts  are  sufficient  to  reduce  large  quantities  of  fat  or  fatty  acids  in  presence 
of  hydrogen.  When  the  reduction  process  is  completed,  the  platinum  metals  or 
their  compounds  can  be  easily  separated  from  the  reduced  fat  or  fatty  acid  by  nitra- 
tion, and  used  again. 

To  prevent  the  formation  of  free  acid,  as,  for  example,  hydrochloric  acid  from  the 
chlorides  of  the  platinum  metals,  in  the  reducing  process,  there  is  added  to  the 
powdered  platinum  salt  a  neutralizing  agent,  such  as  anhydrous  soda,  in  sufficient 
quantity  to  combine  with  the  liberated  acid.  The  employment  of  salts  of  the 
platinum  metals  assists  the  reduction  process  considerably  more  than  is  done  by 
palladium  black  or  platinum  black  containing  an  amount  of  platinum  metal  equal 
to  that  in  the  platinum  metal  salts  used  in  the  present  method.  Thus,  for  example, 
1.7  parts  of  PdCl2  ( =  1  part  of  Pd)  in  presence  of  hydrogen  will  convert  10,000  parts 
of  fat  or  fatty  acid  into  solid  masses  within  3  or  4  hours.  If,  however,  the  PdCl2  be 


100  THE   HYDROGEN ATION   OF  OILS 

replaced  by  a  quantity  of  palladium  black  containing  the  same  amount  of  palladium, 
then,  with  a  ratio  of  1  part  of  Pd  to  10,000  parts  of  fat  or  fatty  acid,  these  substances, 
according  to  Paal,  will  remain  liquid,  even  when  the  palladium  and  hydrogen  are 
allowed  to  act  for  twice  or  three  times  as  long  as  with  PdCl2. 

Paal  notes  that  the  time  required  for  the  reduction  depends  on  the  amount  of 
the  platinum  metal  salt  used,  and  on  the  pressure  under  which  the  hydrogen  is 
allowed  to  act.  By  using  a  palladium  salt  as  the  hydrogen  carrier,  about  50,000 
parts  of  fat  or  unsaturated  fatty  acid  can  be  hydrogenated  within  from  6  to  8  hours 
with  a  quantity  of  salt,  for  example,  PdCl2,  corresponding  with  1  part  of  Pd. 

Paal  gives  the  following  example:  One  million  parts  by  weight  of  castor  oil  or 
oleic  acid  are  treated  with  thirty-four  parts  by  weight  of  dry  palladium  protochloride 
( =  20  parts  of  Pd)  in  the  form  of  powder,  with  or  without  the  equivalent  amount  of 
anhydrous  soda;  or  with  140  parts  by  weight  of  dry  platinum  protochloride  (=  100 
parts  of  Pt)  in  the  form  of  powder;  or  172  parts  of  platinum  chloride;  or  230  parts 
of  platinum  hydrochloride,  with  or  without  addition  of  an  equivalent  amount  of 
anhydrous  soda.  The  mixture  is  placed  in  a  pressure  vessel,  from  which  the  air 
is  exhausted  as  completely  as  possible,  and  hydrogen  is  then  admitted  into  the 
vessel  under  a  pressure  of  2  to  3  atmospheres.  The  reduction  mixture  is  kept  in 
motion  by  a  stirring  apparatus.  The  vessel  is  heated  to  about  80°  C.  although  the 
reduction  may  also  be  carried  out  at  a  lower  temperature.  The  progress  of  the 
reduction  and  the  consumption  of  hydrogen  is  revealed  by  the  fall  in  pressure  as 
indicated  by  the  pressure  gauge.  When  the  gauge  registers  only  a  low  pressure, 
a  fresh  quantity  of  hydrogen  is  admitted.  The  completion  of  the  reduction  process 
can  be  recognized  by  the  gas  pressure  remaining  constant  for  some  considerable 
time.  When  the  reduction  is  ended,  the  reduction  product  is  freed  from  the  catalyzer 
in  a  filter  press  which  is  adapted  to  be  heated. 

The  work  in  the  field  of  catalytic  reduction  of  organic  compounds 
has  been  rather  comprehensively  covered  in  a  publication  by  Skita 
entitled  "  Uber  Katalytische  Reduktionen  Organischer  Verbindungen 
(Stuttgart,  1912).  Skita  has  taken  out  a  patent  assigned  to  Boeh- 
ringer  and  Son  *  which  is  concerned  with  the  hydrogenation  of  organic 
compounds  with  the  aid  of  catalyzers  consisting  of  salts  of  the  plati- 
num group  of  metals.  The  protective  colloid  previously  employed 
he  now  finds  to  be  unnecessary.  He  states  he  has  found  that  an  un- 
saturated substance  can  be  hydrogenated  when  there  is  added  to  it, 
or  its  solution  or  suspension,  a  small  amount  of  palladium  chloride 
or  any  other  soluble  salt  of  a  platinum  metal  and  the  whole  exposed 
to  hydrogen,  most  advantageously  under  pressure.  The  addition  of 
an  acid  is  usually  advantageous  in  this  operation  and  hydrochloric 
acid  is  recommended;  but  with  fatty  bodies  it  suffices  merely  to  add  a 
simple  aqueous  solution  of  a  compound  of  a  metal  of  the  platinum 
group.  As  an  example,  he  states,  that  50  grams  of  olive  oil  may  be 
suspended  in  a  solution  containing  about  0.05  gram  of  platinum 
chloride,  20  cc.  of  alcohol,  50  cc.  of  water  and  8  cc.  of  dilute  hydro- 

*  U.  S.  Patent  1,063,746,  June  3,  1913. 


THE  RARE  METALS  AS  CATXti^ZETRS  '••:":-:'*:  :ftf 


chloric  acid.  After  treatment  with  hydrogen  at  a  pressure  of  about 
4  atmospheres  and  at  a  temperature  of  70°  C.  a  solid  fat  results. 
In  another  example  about  250  grams  of  castor  oil  is  well  mixed 
with  a  solution  of  about  0.05  gram  of  palladium  chloride  in  5  cc.  of 
water.  The  whole  may  then  be  treated  at  about  70°  C.  in  an  auto- 
clave with  constant  stirring,  with  hydrogen  under  a  pressure  of  4 
atmospheres.  After  two  and  one-half  hours  the  oil  will  be  found  so 
far  hydrogenated  that  it  will  solidify  to  a  hard  mass  on  cooling.* 

In  an  address  before  the  Chemical  Society  of  Karlsruhe  Dr.  Skita 
made  the  following  comments  on  the  hydrogenation  of  organic 
material.! 

He  stated  that  the  acceleration  which  various  reactions  experience 
in  the  presence  of  catalyzer  is  the  more  rapid  the  greater  the  surface 
of  the  catalyzer.  As  a  result  a  catalyzer  in  solution  is  always  more 
active  than  is  the  case  when  the  catalyzer  is  in  a  finely-divided  or  pre- 
cipitated state.  This  especially  is  true  with  metals  of  the  platinum 
group  which  exert  an  action  of  a  very  marked  character  when  in  solu- 
tion in  the  colloidal  condition. 

Colloidal  platinum  was  first  produced  by  Bredig  by  the  action  of  an 
electric  current  on  metallic  platinum  in  aqueous  or  ethereal  solution. 
Bredig  recognized  the  property  which  these  colloidal  solutions  pos- 
sessed of  serving  as  a  carrier  for  hydrogen  and  he  in  fact  reduced 
nitrous  acid  to  ammonia.  Such  colloids  are  not  reversible,  that  is  to 
say  if  the  colloidal  solution  is  evaporated  to  dryness  the  metal  will 
not  again  go  into  solution.  A  metal  colloid  which  is  easily  soluble  in 
water  was  discovered  by  Paal  who  made  use  of  a  water-soluble  pro- 
tective colloid,  namely,  the  sodium  salts  of  protalbinic  or  lysalbinic 

*  The  hydrogenation  of  unsaturated  substances  is  effected,  according  to  Skita, 
by  treatment  with  hydrogen  in  the  presence  of  small  quantities  of  compounds  of 
metals  of  the  platinum  group  in  solution.  The  substances  to  be  hydrogenated  may 
be  dissolved  or  suspended  in  a  liquid  (French  Patent  447,420,  Aug.  20,  1912;  also 
British  Patent  28,754,  Aug.,  1912,  and  addition  to  the  latter  Patent  18,996  (1912). 
A  solution  of  palladium  chloride  acidulated  with  dilute  hydrochloric  acid  was 
used  by  Skita  as  a  catalytic  solution  for  the  treatment  of  camphene.  Hydrogen  was 
used  under  a  pressure  of  one  atmosphere.  The  hydrogenation  of  olive  and  castor 
oil  in  this  manner  is  described.  In  the  addition  patent  Skita  states  that  the  employ- 
ment of  dilute  acid  is  not  always  necessary  since  in  many  cases  the  reaction  can  be 
carried  out  simply  by  passing  hydrogen  through  a  mixture  of  the  substances  to  be 
reduced  and  a  solution  of  the  salt.  J.  S.  C.  I.,  March  15,  1913,  253. 

Skita  (Chem.  Zeit.  Rep.  (1913),  680;  British  Patents  18,996,  1912,  and  16,283, 
1913)  carries  on  reduction  processes  without  the  addition  of  any  acid  to  a  solu- 
tion of  a  salt  of  the  platinum  group  and  also  makes  use  of  colloidal  solutions  of  an 
hydroxide  of  the  platinum  group  as  a  catalyzer. 

t  Seifen.  Ztg.  (1913),  960. 


HYDROGENATION  OF  OILS 

acids,  to  maintain  the  metallic  platinum  or  palladium  in  a  water- 
soluble  condition.* 

With  colloids  of  this  character  prepared  from  palladium  Paal  suc- 
ceeded in  adding  hydrogen  to  a  large  number  of  unsaturated  aliphatic 
compounds  which  were  soluble  in  water  or  dilute  alcohol.  For  the 
reduction  of  many  organic  compounds,  such  as  acids,  bases  and  hydro- 
carbons, the  presence  of  acid  material  is  of  importance  and  accordingly 
Skita  has  used  an  acid-stable  protective  colloid  such  as  gum  arabic  in 
place  of  the  sodium  salts  mentioned  above.  If  gum  arabic  is  added 
to  a  solution  of  platinum  chloride,  no  platinum  hydroxide  is  precipi- 
tated when  carbonate  of  soda  is  added  to  the  solution,  for  the  platinum 
remains  suspended  in  the  colloidal  condition. 

By  careful  evaporation  platinum  compounds  may  be  obtained  as 
black  plates  or  scales  which  are  soluble  in  water  and  dilute  acids. 
When  these  colloidal  solutions  of  the  hydroxide  are  agitated  in  the 
presence  of  hydrogen  a  very  acid-resistant  form  of  colloidal  platinum 
results.  ,  On  evaporation  a  form  of  platinum  is  obtained  which  is 
easily  soluble  in  water.  All  such  platinum  and  palladium  compounds 
are  eminently  adapted  to  catalytically  transfer  hydrogen  to  unsatu- 
rated material  contained  in  an  acid  or  neutral  vehicle.  It  is  especially 
easy  to  add  hydrogen  to  the  double  bonds  of  aliphatic  and  hydrocyclic 
hydrocarbon  compounds.  This  is  the  case  as  regards  the  reduction 
of  alkaloids. 

Another  interesting  observation  is  that  very  stable  colloidal  solu- 
tions of  platinum  may  be  obtained  readily  by  passing  hydrogen 
through  such  colloidal  solutions  of  platinum  containing  gum  arabic, 
even  when  the  solution  is  cold.  In  a  similar  manner  colloidal  solu- 
tions of  palladium  are  produced  from  palladium  chloride. 

Finally  it  may  be  mentioned  that  in  this  way  hydrogen  may  be 
added  to  aromatic  and  heterocyclic  compounds  which  cannot  be 
hydrogenated  with  platinum  black  catalyzer. f 

*  Colloidal  solutions  of  gold,  silver,  platinum,  palladium,  copper,  lead,  iron,  zinc, 
tin,  nickel,  aluminum,  magnesium,  bismuth,  antimony  and  cadmium,  respectively, 
have  been  prepared  with  great  ease  by  an  electrical  disintegration  method,  using 
a  high-frequency  alternating  arc,  the  leads  to  which  were  taken  from  two  points 
on  the  inductance  of  the  oscillatory  circuit  of  a  Poulsen  arc  as  used  in  wireless  teleg- 
raphy. By  varying  the  conditions  it  was  possible  to  obtain  currents  of  from  0.14 
to  15  amperes  and  E.M.F.  of  480  to  4080  volts,  and  colloidal  solutions  showing 
a  wide  range  of  colors  were  thus  obtained  from  a  number  of  the  metals.  (Morris- 
Airey  and  Long,  Proc.  Univ.  Durham  Phil.  Soc.  (1912-1913),  5,  68;  J.  S.  C.  I.  (1913), 
1015.) 

f  In  his  dissertation  entitled  "tiber  katalytische  Hydrierungen  organischer  Ver- 
bindungen  mit  kolloidem  Palladium  und  Platin,"  Meyer  draws  the  following  con- 


THE  RARE  METALS  AS  CATALYZERS  103 

Colloidal  suspensions  of  the  metals  *  have  proved  excellent  cata- 
lyzers, effecting  many  of  the  reactions  which  are  brought  about  by 
enzymes.  The  analogy  between  the  action  of  the  finely-divided  metals 
and  the  organic  enzymes  is  strikingly  illustrated  by  the  behavior  of 
poisons  on  the  two.  The  same  substances  which  poison  the  ferments 
and  which  retard  the  rate  at  which  they  decompose  hydrogen  dioxide, 
also  poison  platinum  and  retard  the  rate  at  which  it  effects  the  same 
decomposition.  Thus  mercuric  chloride  and  hydrocyanic  acid  in 
the  merest  traces  poison  the  organic  enzymes.  The  same  quantities 
produce  almost  exactly  the  same  effect  on  the  finely-divided  metals, 
with  respect  to  their  power  to  decompose  hydrogen  dioxide.f 

elusions.  Methods  of  reduction  depending  on  the  use  of  a  solution  of  palladious 
chloride  and  gum  arabic  in  water-alcohol  mixture,  forming  colloidal  palladium  with 
hydrogen,  do  not  progress  satisfactorily  unless  bodies  are  present  which  are  capable 
of  forming  addition  compounds  with  palladious  chloride.  The  action  of  hydrogen 
on  a  hot  solution  of  palladium  chloride  and  a  protective  colloid  gives  rise  to  a  colloidal 
solution  of  palladium.  From  colloidal  palladium  or  platinum  solutions  using  gum 
arabic  or  gelatine  as  a  protective  colloid,  the  corresponding  reversible  metal  colloid 
is  obtained.  With  the  aid  of  gum  arabic  or  gelatine  as  a  protective  colloid  it  is 
possible  to  obtain  permanent  colloidal  solutions  of  palladium  and  platinum  hydrox- 
ide. By  careful  evaporation  and  drying  of  these  colloidal  solutions  solid  products 
are  obtained  which  may  be  brought  again  into  colloidal  solution  by  peptization. 
Stable  colloid  solutions  of  palladium  may  be  advantageously  obtained  by  the  reduc- 
tion of  dialyzed  colloid  palladious  hydroxide  solutions.  For  the  production  of  a 
colloidal  solution  of  platinum  it  is  recommended  that  reduction  of  chlorplatinic  acid 
by  hydrogen  in  the  presence  of  a  protective  colloid  be  employed,  in  which  case  the 
mixture  should  first  be  inoculated  with  small  amounts  of  colloidal  platinum  or 
palladium.  Colloidal  solutions  of  platinum  and  palladium  with  gum  arabic  or 
gelatine  as  a  protective  colloid  are  well  adapted  to  the  hydrogenation  of  olefine 
bodies.  The  hydrogenation  of  aromatic  bodies  with  colloidal  metallic  platinum  is 
possible  only  in  strong  acetic  acid  solutions.  The  hydrogenation  of  aromatic  bodies 
is  carried  out  more  easily  with  platinum  than  with  palladium.  While  gum  arabic 
is  suitable  for  use  as  a  protective  colloid  with  platinum  or  palladium  in  the  hydro- 
genation of  certain  organic  bodies,  it  is  found  that  gelatine  under  some  conditions 
acts  as  a  catalyzer  poison.  Vulcanized  rubber  also  affects  the  activity  of  the  cata- 
lyzer. The  inoculation  method  for  the  production  of  colloidal  solutions  of  platinum 
affords  a  convenient  laboratory  procedure  for  the  hydrogenation  of  aromatic  bodies 
as  the  formation  of  the  colloidal  solution  and  the  process  of  hydrogenation  follow 
one  another  quickly.  The  hydrogenation  of  aromatic  bodies  using  colloidal  platinum 
as  a  catalyzer  progresses  three  or  four  times  quicker  than  when  platinum  black  is 
employed.  See  also  J.  S.  C.  I.  (1913),  46,  and  Ber.  (1912),  45,  3379. 

A  solution  of  colloidal  platinum  is  capable  of  causing  the  union  of  hydrogen  and 
oxygen.  (Ernst,  Zeitsch.  physikal.  Chem.  (1901),  37,  448.)  Ethylene  unites  with 
hydrogen  even  in  the  cold,  in  the  presence  of  platinum  sponge.  (De  Wilde,  Ber.  7, 
354.) 

*  Jones,  A  New  Era  in  Chemistry. 

t  Measurements  have  shown  that  the  decomposition  of  hydrogen  dioxide  by  metals 


104  THE  HYDROGENATION   OF  OILS 

Karl  *  has  studied  with  considerable  care  and  in  a  quantitative  way 
the  action  of  palladium  supported  on  various  bodies.  He  found  that 
palladium  precipitated  on  finely-divided  nickel  or  magnesium  proved 
effective  catalytically,  while  if  precipitated  on  lead,  aluminum,  iron, 
or  zinc,  little  or  no  hydrogenation  was  effected,  owing  to  the  anti- 
catalytic  action  of  these  metals.  While  metallic  zinc  is  anticatalytic, 
zinc  oxide  and  carbonate  have  no  such  effect.  In  these  investigations 
Karl  worked  principally  with  fish,  cotton  and  castor  oil  and  oleic  acid.f 

is  a  reaction  of  the  first  order,  that  is,  the  metal,  strictly  speaking,  does  not  enter  into 
the  reaction  at  all,  only  the  mass  of  hydrogen  dioxide  present  undergoing  change. 

A  hydrogenizing  ferment  in  the  animal  organism  capable  of  transforming  nitro- 
benzene into  aniline  has  been  observed  by  Abelous  and  Gerard  (Comptes  Rend., 
130  (7),  420).  A  clear  aqueous  extract  of  horse's  liver,  in  presence  of  chloroform 
and  in  an  atmosphere  of  hydrogen,  reduced  nitrobenzene  to  aniline,  while  the  same 
extract,  previously  boiled,  was  without  action.  Abelous  and  Gerard  have  previously 
shown  (J.  S.  C.  I.,  1899,  871)  the  deoxidizing  action  of  this  ferment,  but  have  had 
no  instance  of  hydrogenation  under  its  influence.  (See  also  Chandler,  J.  S.  C.  I., 
1913,  73.) 

*  Inaugural  Dissertation,  Erlangen,  1911. 

t  Paal  and  Karl  (Ber.  (1913),  3069;  Chem.  Ztg.  Rep.  (1913),  642)  tested  palla- 
dium on  various  carriers  as  catalytic  material  for  hardening  fats  and  have  found 
that  the  oxides,  hydroxides  and  carbonates  of  lead,  cadmium,  zinc,  aluminum  and 
iron  have  an  anti-catalytic  action  similar  to  the  metals  which  they  contain.  The 
corresponding  compounds  of  nickel  and  cobalt,  and  also  magnesium  oxide,  were  in- 
vestigated. These  carriers  were  coated  with  palladium  by  mixing  with  a  solution 
of  palladium  chloride  in  a  weak  aqueous  solution  of  hydrochloric  acid  at  room  temper- 
ature, or  slightly  warmed.  Palladious  hydroxide  was  thus  precipitated  and  reduc- 
tion was  obtained  by  treatment  of  the  powder,  which  was  first  moistened  with 
ether,  to  the  action  of  hydrogen  at  room  temperature.  The  catalyzer  was  mixed 
with  fatty  material  without  permitting  contact  with  the  air  and  reduction  was 
carried  out  in  an  agitator  in  an  atmosphere  of  hydrogen.  Magnesium  oxide  did 
not  retard  the  catalytic  action  of  palladium.  In  fact,  the  reduction  process  appeared 
to  be  somewhat  increased  by  the  presence  of  this  material. 

Paal  and  Windisch  carried  on  similar  experiments  with  platinum.  (Ber.  (1913), 
4010.)  Metal  powders  of  various  sorts  were  purified  with  alcohol  and  ether  and  then 
platinized  by  shaking  with  a  solution  of  chlorplatinic  acid.  Metallic  oxides  and 
carbonates  were  platinized  by  the  action  of  sodium  carbonate  and  hydrazine  hy- 
drate on  a  solution  of  chlorplatinic  acid  containing  the  oxide  or  carbonate  in  suspen- 
sion. These  products  as  catalyzers  in  the  hydrogenation  of  cottonseed  oil  were 
found  to  have  differing  degrees  of  catalytic  action,  and  only  nickel  and  magnesium 
had  no  influence  on  the  activity  of  the  platinum.  The  platinum  was  much  less 
active  in  the  presence  of  aluminum,  cobalt  and  bismuth,  and  was  rendered  completely 
inactive  by  iron,  copper,  zinc,  silver,  tin  and  lead.  Of  the  oxides  and  carbonates 
examined,  only  the  magnesium  compounds  were  without  influence. 

Wieland  (Ber.  (1912),  45,  2615)  considers  palladium  black  less  sensitive  to 
"poisons"  than  platinum  black,  for  in  presence  of  the  former  a  sample  of  benzene 
containing  thiophen  absorbed  hydrogen  at  a  noticeable  rate  although  not  so  rapidly 
as  pure  benzene. 


THE  RARE  METALS  AS  CATALYZERS  105 

A  long  list  of  salts  available  as  catalyzers  is  given  in  German  Patent 
260,885  *  embracing  the  sulfates,  nitrates  and  chlorides  of  platinum 
and  palladium,  and  double  salts  of  these  with  alkali  chlorides  and 
other  chlorides,  also  certain  complex  compounds  of  these  metals. 
The  salts  are  added  in  an  undissolved  state  directly  to  the  oil  to  be 
hardened  and  subsequently  a  neutralizing  agent  also  undissolved  is 
added.  The  temperature  is  maintained  below  100°  C.  When  em- 
ploying double  salts  care  should  be  taken  to  have  no  anticatalytic 
substances,  such  as  lead,  present  in  the  mixture.  Salts,  such  as  acid 
oxalate  of  platinum,  whose  acid  radical  is  capable  of  reduction,  may 
be  used.f  If  necessary,  a  solid  neutralizing  agent  may  be  added  (cf. 
Paal). 

The  Seifenseider  Zeitung,  1912,  550,  makes  mention  of  a  German 
Patent  application  for  a  process  of  making  hardened  fats,  using  as 
catalyzers  platinum  and  platinum  hydroxide  in  the  form  of  precipi- 
tates and  on  inert  carriers  in  place  of  the  corresponding  compounds  of 
palladium. 

In  order  to  avoid  the  accidental  introduction  of  air  or  mercury  when  reducing 
by  means  of  hydrogen  and  colloidal  platinum  a  special  apparatus  has  been  constructed 
by  Stark  (Ber.  1913  (46),  2335).  It  consists  of  a  glass  vessel  with  two  necks,  each 
provided  with  a  glass  stopcock.  A  small  funnel  with  a  stopcock  is  fused  into  the 
upper  part  of  the  vessel  between  the  two  necks.  One  neck  is  connected  with  the 
source  of  hydrogen,  the  other  with  a  graduated  gas  burette  and  mercury  reservoir. 
The  substance  to  be  reduced  is  placed  in  the  glass  vessel  and  a  current  of  hydrogen 
passed  through.  At  this  stage  the  burette  and  reservoir  contain  no  mercury.  The 
hydrogen  supply  is  then  cut  off  and  mercury  is  poured  into  the  reservoir  from  which 
it  flows  and  partly  fills  the  burette.  By  lowering  the  reservoir  a  solution  of  platinum 
or  palladium  can  be  introduced  through  the  funnel  with  the  stopcock  without  ad- 
mitting any  air. 

Lehmann  carries  out  the  hydrogenation  of  oils  or  unsaturated  fatty 
acids  by  passing  hydrogen  through  oil  containing  a  small  amount  of 
osmium  tetroxide,  while  the  oil  is  being  heated.  Osmium  dioxide 
forms  from  the  tetroxide,  producing  a  colloidal  solution  which  can  be 
removed  by  animal  charcoal.  In  one  experiment  10  grams  olive  oil 

Cf.  Windisch,  Ueber  die  Hydrogenisation  ungesattigter  organischer  Verbindun- 
gen  durch  Platin  und  Palladium-wasserstoff  und  die  antikatalytische  Wirkung  von 
Fremdstoffen  auf  den  Hydrogenisierungsprozess.  Erlangen,  1913. 

Dissertation:  Schwarz,  Erlangen,  1913,  publishes  work  on  colloidal  platinum 
and  the  effect  of  anti-catalytic  bodies.  J.  v.  Bergen,  Karlsruhe,  1913,  gives  results 
of  work  with  palladium  hydrosols. 

*  Seifen.  Ztg.,  1913,  851. 

t  Fokin  has  used  the  compound  PdCh.2  NaCl  as  a  catalyzer  (Russian  Patent 
22,629,  Sept.  30,  1912;  Chem.  Ztg.  Rep.,  1914,  40). 


106  THE  HYDROGENATION  OF  OILS 

with  0.05  gram  osmium  tetroxide  produced  in  1 J  hours  a  fat  of  melting 
point  39°  C.  It  is  not  necessary  to  use  hydrogen  under  pressure.* 

Besides  palladium  and  platinum  the  metals  iridium,  rhodium, 
ruthenium  and  osmium  are  specified  as  catalytic  material.!  Madina- 
veitiat  has  studied  the  catalytic  activity  of  ruthenium,  rhodium,  iridium 
and  osmium  black. 

In  connection  with  the  volumetric  determination  of  hydrogen  by 
catalytic  absorption  in  a  solution  of  sodium  picrate  and  colloidal  pal- 
ladium Paal  and  Hartmann  §  note  that  oxygen  and  unsaturated  hydro- 
carbons must  be  removed,  for  in  presence  of  palladium,  hydrogen 
reacts  with  them  to  form  water  and  paraffin  hydrocarbons  respectively; 
and  carbon  monoxide  should  also  be  removed,  as  it  acts  as  a  "  poison  " 
on  the  catalyst,  and  greatly  retards  the  absorption. 

Colloidal  solutions  of  hydroxides  of  metals  of  the  platinum  group,  obtained  by 
treating  a  solution  of  a  salt  of  the  metal  with  sodium  carbonate  in  presence  of  gum 
arabic,  are  found  by  Skita  (British  Patent  16,283,  July  15,  1913)  to  be  efficient  hydro- 
gen carriers  in  the  hydrogenation  of  unsaturated  compounds,  the  reaction  being 
possible  even  in  neutral  solutions.  In  this  manner  it  is  stated  that  unsaturated 
fatty  acids  or  fats  can  be  hydrogenated  to  any  degree.  For  example,  a  hard  fat 
is  obtained  by  passing  hydrogen  at  a  pressure  of  seven  atmospheres  into  a  mixture 
of  50  parts  (by  weight)  of  peanut  oil  and  60  parts  of  a  colloidal  solution  of  palla- 
dious  hydroxide,  containing  about  0.07  part  of  the  hydroxide,  at  a  temperature  of 
60°  C. 

*  Arch.  Pharm.  (1913),  152;  Seifen.  Ztg.  (1913),  418. 

t  Vereinigte  Chemische  Werke  A.  G.  French  Patent  425,729  (1911);  Seifen.  Ztg. 
(1912),  390. 

In  using  platinum  or  palladium  the  following  example  is  given:  1000  kilos  castor 
oil  are  mixed  with  1  kilo  of  catalyzer  which  contains  1  per  cent  of  palladium  or 
2  per  cent  platinum  either  in  the  metallic  state  or  in  the  form  of  the  lower  hydroxide. 
This  mixture  of  oil  and  catalyzer  is  placed  in  a  closed  receptacle  equipped  with  an 
agitator.  Any  moisture  present  is  removed  as  completely  as  possible  and  then 
hydrogen  is  introduced,  creating  a  gas  pressure  of  2  to  3  atmospheres.  The  contents 
of  the  receptacle  are  heated  to  80°  C.  and  the  agitator  put  into  operation.  Hydro- 
gen is  introduced  as  required.  The  hydrogenation  of  fatty  acids  may  be  carried 
out  in  a  similar  manner,  but  care  should  be  taken  to  use  catalytic  material  contain- 
ing palladium  or  platinum  which  is  not  attacked  by  acids.  One  composition  men- 
tioned for  the  purpose  is  prepared  by  mixing  barium  chloride  with  palladium  or 
platinum  chloride  to  which  is  added  sodium  sulfate  and  some  hydroxylamine  or 
other  reducing  agent.  For  the  production  of  oleic  acid  one  part  of  catalyzer  carry- 
ing 1  per  cent  of  palladium  or  2  per  cent  platinum  is  used  to  1000  parts  of  the  fatty 
acid. 

Palladium  in  various  metallic  forms  as  a  catalyzer  is  mentioned  in  Seifen.  Ztg. 
(1914),  7,  as  forming  a  basis  of  a  patent  application  by  the  Naamlooze  Vennootschap 
Ant.  Jurgens  Vereenigde  Fabrieken.  See  German  Patent  272,340,  1912. 

t  Chem.  Abs.,  1914,  1106. 

§  Ber.  (1910),  43,  243. 


THE  RARE  METALS  AS  CATALYZERS  107 

Thron  *  adds  hydrogen  to  unsaturated  bodies  with  the  aid  of  a 
finely-divided  metal  of  the  platinum  group  and  formic  acid.  The 
latter  is  split  by  the  platinum  metals  by  catalytic  action  into  carbonic 
acid  and  hydrogen,  the  latter,  it  is  stated,  causing  the  formation  of  a 
compound  of  the  platinum  metal  and  hydrogen  (hydride  of  the  plati- 
num metal).  By  adding  to  the  substance  to  be  hydrogenized  formic 
acid  and,  for  example,  palladium  black,  the  development  of  carbonic 
acid  begins  at  once,  while  hydrogen  is  combined  with  the  unsaturated 
bodies  present. 

A  platinum  catalyzer  used  by  Porter  (U.  S.  Patent  684,863,  Oct.  22,  1901)  for 
igniting  combustible  gas  is  prepared  by  mixing  platinum  black  with  the  oxide  of 
zirconium  in  about  the  proportion  of  twenty-five  per  cent  of  platinum  to  seventy- 
five  per  cent  of  zirconium  oxide.  To  prepare  this,  the  platinum  in  a  state  of  solu- 
tion is  mixed  with  the  oxide  of  zirconium  and  the  liquid  is  evaporated,  leaving  the 
platinum  compound  distributed  throughout  the  mass.  This  is  then  applied  to  some 
incombustible  substance,  such  as  asbestos  or  mineral  wool,  which  forms  a  convenient 
support  for  the  substance.  After  heating,  the  platinum  remains  in  a  finely-divided 
state,  de  Montlaur  used  mica  as  a  support  for  platinum,  Zeitsch.  f.  angew.  Chem. 
(1914),  61,  No.  7. 

A  catalyzer  capable  of  bringing  about  reaction  between  air  and  ammonia  to  form 
nitric  oxide  has  been  proposed  by  Schick  (U.  S.  Patent  971,149,  Sept.  27,  1910) 
and  is  based  on  the  use  of  platinum  coated  on  a  suitable  carrier  such  as  quartzite, 
porcelain  and  the  like.  The  spongy  form  of  platinum  is  not  useful  for  the  pur- 
pose, owing  to  undesirable  side  reactions  taking  place  in  the  center  of  the  spongy 
mass.  Accordingly  a  very  thin  surface  layer  of  platinum  is  deposited  on  the  carrier, 
and  to  get  a  coating  of  sufficient  thickness  the  carrier  is  coated  with  a  glaze  such  as 
a  mixture  of  felspar  and  an  alkali  that  will  soften  easily  when  heated.  The  platinum 
material  is  then  baked  on  the  carrier  in  the  presence  of  this  glaze  which  brings  about 
the  formation  of  a  uniformly  thin  layer  of  the  metal.  A  temperature  of  1400°  C. 
is  used. 

In  discussing  the  properties  of  platinum  as  a  contact  material  for  igniting  com- 
bustible gas,  Perl  (U.  S.  Patent  615,363,  Dec.  6,  1898)  states  that  after  the  dis- 
covery that  finely-divided  platinum  did  not  fulfil  the  requirements,  the  endeavor 
was  made  to  increase  the  effect  of  the  finely-divided  platinum  by  mingling  the  same 
with  different  porous  bodies,  according  to  the  suggestion  of  Liebig  (Pogg.  Ann., 
Vol.  17  (1829),  107).  Dobereiner  (Journ.  Praktischer  Chemie,  1839,  Vol.  17,  158) 
went  further  and  prepared  finely-divided  platinum  within  the  pores  of  natural  or 
artificial  meerschaum  or  clay.  Perl  regards  a  method  of  this  character  to  bring 
about  the  formation  of  chloride  of  magnesium  or  other  earths,  because  by  reduction 
of  the  platinum  salts  which  are  in  the  pores  of  the  employed  material  a  part  of  the 
latter  is  always  transformed  by  the  action  of  the  acids  freed  from  the  platinum 
salts  (chiefly  hydrochloric  acid)  into  compounds  which  are  injurious  on  account  of 
-their  hygroscopic  properties,  and  which  act  as  fluxes,  causing  the  igniting  material 
to  become  denser  and  more  impenetrable  for  the  gas  after  a  short  time.  To  meet 
these  objections  Perl  proceeds  as  follows: 

Porous  combustible  material  is  thoroughly  mingled  with  a  solid  or  dissolved 
platinum  salt.  The  mixture  is  dried  at  a  moderate  temperature,  and  the  platinum 

*  U.  S.  Patent  1,077,442,  Nov.  4,  1913. 


108  THE  HYDROGENATION  OF  OILS 

is  reduced  in  the  pores  of  the  incombustible  material  by  bringing  the  mixture  to  a 
high  degree  of  heat  in  a  covered  crucible  until  the  hydrochloric  acid  or  the  vapors 
of  any  other  acid  have  disappeared.  The  same  result  is  also  brought  about  by 
heating  the  mixture  in  a  reducing  gas  flame.  The  residual  salts  are  now  extracted 
with  diluted  hydrochloric  acid  and  subsequently  with  water  until  all  trace  of  any 
soluble  salts  removed. 

Efrem  (British  Patent  14,339,  1899;  J.  S.  C.  I.,  1900,  726)  and  Chem.  Fab.  vorm. 
Goldenberg  (British  Patent  618,  1900;  J.  S.  C.  I.,  1901,  250)  employ  clay  and  simi- 
lar supporting  material  for  platinum  in  preparing  catalytic  material.  (See  also 
British  Patents  6448,  1905;  J.  S.  C.  I.,  1906,  432  and  10,729,  1901;  J.  S.  C.  I.,  1902, 
548.) 

C.  E.  Munroe  (U.  S.  Patent  724,317,  March  31,  1903)  produces  a  form  of  plat- 
inum contact  material  active  in  oxidation  processes  by  causing  the  formation  upon 
perforated  sheets  or  disks  of  asbestos  and  upon  sheets  or  disks  of  perforated  metal 
or  woven  wire  of  a  coating  of  finely-divided  platinum.  For  instance,  a  perforated 
sheet  of  asbestos  is  immersed  in  an  alcoholic  solution  of  ammonium  chloride  and 
then  in  an  alcoholic  solution  of  platinic  chloride,  or,  if  preferred,  the  sheet  may  be 
first  immersed  in  the  platinic  chloride  and  subsequently  in  the  ammonium  chloride, 
forming  upon  the  surface  of  the  asbestos  a  crystalline  precipitate  of  ammonium- 
platinic  chloride.  When  the  precipitate  has  been  formed,  the  sheet  of  asbestos  is 
heated.  The  heat  acts  first  to  drive  off  the  alcohol  and  then  decomposes  the  double 
platinum  salt,  leaving  the  metal  in  a  very  finely-divided  state. 

Paal  and  Amberger  *  describe  the  production  of  preparations  of  a 
greasy  consistency  containing  inorganic  metal  colloids  of  the  platinum 
group,  consisting  in  incorporating  solutions  of  the  divalent  salts  of  the 
metals  of  the  platinum  group  with  bodies  maintaining  colloids  in 
the  colloidal  state  (protecting  colloids)  especially  with  wool  fat  or  the 
alcohols  obtainable  therefrom  by  saponification,  and  adding  a  carbon- 
ate of  an  alkali  to  form  the  colloidal  lower  hydroxides  of  the  metals 
employed.  They  note  that  preparations  containing  combinations  of 
the  divalent  salts  of  the  metals  of  the  platinum  group  in  a  colloidal 
condition  can  be  obtained,  if,  instead  of  the  alkali  carbonates  used 
above,  the  alkali  salts  of  certain  weak  organic  acids  are  selected,  for 
instance,  the  salts  of  the  higher,  saturated,  or  unsaturated,  fatty 
acids  (soaps).  In  this  way  there  are  produced  in  the  presence  of 
solutions  of  the  metal  salts,  for  instance,  of  divalent  palladium,  or 
platinum,  triturated  with  wool  fat,  products  which  contain  the  corre- 
sponding palladium,  or  platinum,  salts  dissolved  in  colloidal  form  in 
the  wool  fat. 

If,  according  to  Paal  and  Amberger,  wool  fat  be  impregnated  with  a  concentrated 
aqueous  solution  of  palladious  chloride  (PdCU)  and  the  mass  be  then  triturated  with 
the  equivalent  quantity  of  potassium  oleate  in  concentrated  aqueous  solution,  the 
salts  mutually  decompose  with  formation  of  potassium  chloride  and  palladious 
oleate  which  remains  dissolved  in  colloidal  form  in  the  wool  fat.  As  the  palladious 
chloride  is  difficultly  soluble  in  pure  water  but  readily  in  hydrochloric  acid  it  is  dis- 

*  U.  S.  Patent  1,077,891,  Nov.  4,  1913. 


THE  RARE  METALS  AS  CATALYZERS  109 

solved  in  the  latter  and  the  acid  is  neutralized  before  triturating  the  liquid  with  wool 
fat  by  means  of  an  amount  of  sodium  carbonate  equivalent  to  the  hydrochloric 
acid  used.  The  neutral  PdCl2  then  remains  dissolved  in  the  liquid. 

In  order  to  obtain  a  preparation  containing  about  25  per  cent  colloidal  palladious 
oleate  0.85  part  of  palladious  chloride  PdCl2  =  0.5  part  of  palladium  are  dis- 
solved with  the  application  of  heat  in  0.45  part  of  fuming  hydrochloric  acid  (38  per 
cent  HC1)  and  2  parts  of  water,  and  the  hydrochloric  acid  is  neutralized  by  the  addi- 
tion of  0.3  part  of  anhydrous  soda  either  solid  or  dissolved  in  0.7  part  of  water. 
The  solution  of  PdCl2  thus  obtained  is  then  triturated  intimately  in  small  portions 
with  9.5  parts  of  wool  fat  softened  at  a  gentle  heat.  Into  the  body  thus  obtained 
are  then  stirred,  also  in  small  portions,  3.5  parts  of  potassium  oleate  dissolved  in 
15  parts  of  water.  The  formation  of  the  palladium  oleate  is  detected  by  the  fact 
that  the  greasy  mass  colored  red-brown  by  the  palladious  chloride  becomes,  on 
being  triturated  with  the  potassium  oleate,  first  yellow-brown,  then  gray-brown  and, 
after  being  allowed  to  stand  some  considerable  time,  black-brown.  To  purify  the 
product  it  may  be  either  treated  repeatedly  with  hot  water  at  from  50°  to  60°  C., 
and  the  mass  exposed  in  vacuo  at  from  40°  to  50°  C.,  for  the  purpose  of  removing 
the  water;  or  the  original  product  may  be  dissolved  in  from  5  to  6  times  its  vol- 
ume of  petroleum  ether  of  low  boiling  point,  the  greater  part  of  the  by-products 
remaining  undissolved  and  the  red-brown  liquid  organosol  being  dried  with  calcium 
chloride  or  dehydrated  sodium  sulfate.  In  this  case  a  further  part  of  the  by-products 
separates  along  with  the  water.  The  petroleum  ether  is  then  distilled  off  from  the 
liquid  freed  from  the  drying  agent.  The  colloidal  palladium  oleate  can  be  enriched 
in  the  "ointment"  body  by  solution  in  petroleum  ether  and  precipitation  with 
alcohol.  A  product  is  thus  obtained  containing  about  70  per  cent  of  colloidal 
palladium  oleate,  which  like  the  25  per  cent  preparation,  is  absorbed  as  organosol  by 
all  organic  substances  dissolving  wool  fat.  Instead  of  a  palladious  salt,  a  platinous 
or  other  salt  of  the  platinum  group  can  be  used,  for  instance,  the  salt  of  divalent 
platinum  resulting  from  the  reduction  of  the  platinochloride-hydrochloric  acid  with 
sulfur  dioxide.  Wool  fat  impregnated  with  platinous  salt,  when  acted  on  by  an 
aqueous  solution  of  potassium  oleate,  forms  a  colloidal  platinous  oleate  (CisHasC^jPt. 
A  mixture  of  the  wool  fat  alcohols  obtained  from  wool  fat  by  saponification  can  be 
used  in  the  same  manner  as  wool  fat.  The  wool  fat  alcohols  are  in  their  properties 
very  similar  to  the  wool  fat  itself  and  the  mixture  of  alcohols  obtained  therefrom  by 
saponification  presents  a  still  greater  affinity  for  water  than  wool  fat.  The  wool 
fat  alcohols  have  a  more  solid  consistency  than  the  wool  fat.* 

Meyer  f  reports  an  experiment  on  the  hydrogenation  of  olive  oil 
with  a  colloidal  palladium  hydroxide  solution  containing  0.2  gram 

*  Amberger  (Kolloid-Zeit.  (1913),  13,  310)  has  prepared  organosols  of  palladium, 
platinum,  palladious  hydroxide,  palladium  oleate  and  platinous  hydroxide.  In  the 
preparation  of  the  metallic  organosols,  hydrazine  hydrate  was  used  as  a  reducing 
agent.  The  palladium  organosols  (8  :  9  to  16  per  cent  Pd)  had  pronounced  catalytic 
activity;  small  quantities  dissolved  in  fatty  oils  were  capable  of  transferring  hydro- 
gen to  the  unsaturated  glycerides  of  the  oil,  with  the  formation  of  so-called  hardened 
oils.  The  platinum  organosols  contained  8.14  to  18.4  per  cent  Pt.  The  hydroxide 
organosols  were  prepared  by  the  interaction  of  the  corresponding  chlorides  and  sodium 
carbonate  and  the  palladium  oleate  organosols  from  the  chloride  and  potassium 
oleate  in  presence  of  wool  fat.  (J.  S.  C.  I.  (1914),  41.) 

t  Dissertation,  Karlsruhe,  1912. 


110  THE  HYDROGENATION  OF  OILS 

palladium  and  0.34  gram  gum  arable  in  100  cc.  Two  volumes  of 
olive  oil  to  one  volume  of  the  colloidal  solution  were  heated  and  agita- 
ted in  an  autoclave  at  a  temperature  of  70°  to  80°  C.  under  a  hydrogen 
pressure  of  6  atmospheres.  Hydrogen  was  added  to  replace  that 
absorbed.  After  one-half  hour  no  further  absorption  of  hydrogen 
could  be  noted,  but  the  agitation  was  continued  for  2  hours.  The  fat 
was  then  separated  from  the  colloidal  solution  and  boiled  with  water. 
A  solid  fatty  product  was  obtained. 

For  the  purpose  of  combining  hydrogen  with  nitrogen  to  make 
ammonia  the  Badische  Anilin  &  Soda  Fabrik  *  recommend  cerium  and 
a  "  promoter  "  as  a  catalytic  agent. 

With  some  exceptions,  compounds  of  the  alkali  metals  and  the  alkaline  earth 
metals  are  said  to  act  as  promoters  of  the  catalytic  power.  Also  oxides  of  the  rare 
earth  metals,  tantalum  and  niobium,  as  well  as  silica,  may  be  employed  as  promoters. 
As  a  general  rule  those  metals  or  compounds  of  the  metals  which  yield  oxides  and 
salts  which  are  non-reducible  by  hydrogen  are  suitable  for  use  as  promoters.  On 
the  other  hand,  the  metalloids,  such  for  instance  as  sulfur,  selenium,  tellurium, 
arsenic,  phosphorus,  and  also  the  easily  fusible  and  easily  reducible  metals,  such  for 
instance  as  lead,  tin  and  zinc,  generally  act  as  contact  poisons,  whether  the  element 
be  added  or  be  present  as  such  or  in  the  form  of  a  compound. 

The  following  example  is  given.  Take  metallic  cerium  which  has  been  prepared 
electrolytically  and  is  in  the  condition  of  small  grains,  and  mix  it  with  about  two 
per  cent  of  its  weight  of  powdered  potassium  nitrate,  and  then  place  the  mixture 
in  the  contact  tube.  On  passing  a  mixture  of  hydrogen  and  nitrogen  through  the 
tube,  while  heating,  a  catalytic  agent  is  obtained  which  is  said  to  give  about  three 
times  the  yield  that  the  untreated  cerium  affords. 

*  U.  S.  Patent  1,068,968,  July  29,  1913. 


CHAPTER  VII 

THE    OCCLUSION   OF   HYDROGEN   AND   THE   MECHANISM 
OF  HYDROGEN  ADDITION 

As  an  acquaintance  with  the  subject  of  hydrogen  addition  and 
reduction  by  hydrogen  of  various  bodies  may  lead  to  a  broader  knowl- 
edge of  catalytic  reactions  in  the  hydrogenation  of  oils,  the  following 
notes  by  various  observers  are  included. 

Sie verts  and  Krumhaar*  did  not  find  hydrogen  to  be  absorbed  by 
the  metals  cadmium,  thallium,  zinc,  lead,  bismuth,  tin,  antimony, 
silver  and  gold.  The  solubility  in  copper,  nickel,  iron  and  palladium 
is  shown  in  the  graphic  curve  diagram.  (Fig.  50.) 

The  curves  show  that  the  solubility  increased  regularly  with  the  temperature  up 
to  the  melting  point  and  then  suddenly  increased,  the  solubility  in  the  liquid  metal 
then  increasing  regularly  in  the  same  manner.  With  palladium,  however,  the 
solubility  was  independent  of  the  temperature  up  to  the  melting  point  and  then 
diminished  to  one-half,  and  in  the  liquid  metal  was  again  independent  of  the  temper- 
ature. On  cooling,  copper  retained  20  per  cent  and  nickel  8  per  cent  of  the  hydrogen 
absorbed,  and  in  the  case  of  iron,  the  evolution  of  gas  was  so  violent  on  solidification 
that  the  tube  was  blown  to  pieces,  leaving  a  spongy  regulus.  In  experiments  with 
alloys  it  was  found  that  the  addition  of  gold  lowered  the  solubility  of  oxygen  in 
silver.  The  copper  alloys  and  hydrogen  formed  three  groups:  (a)  those  in  which 
the  solubility  was  not  influenced,  such  as  silver;  (6)  those  in  which  the  solubility 
was  lowered,  such  as  gold,  tin,  aluminium;  (c)  those  in  which  the  solubility  was 
higher  than  that  accounted  for  by  the  copper  content,  such  as  nickel  and  platinum. 
The  solubility  in  copper  alloys  was  proportional  to  the  square  root  of  the  pressure, 
and  the  view  that  occlusion  was  due  to  adsorption  is  untenable,  and  although  Sieverts 
and  Krumhaar  hold  the  view  that  adsorption  did  not  exist  at  high  temperatures, 
they  do  not  express  any  opinion  about  low  temperature  conditions,  and  they  put 
forward  the  view  that  gases  and  metals  form  solid  and  liquid  alloys,  the  solubility 

of  which  does  not  follow  Henry's  law,  but  is  expressed  by  the  formula         . 

m 

Exhaustive  data  are  given  by  Sieverts  (Z.  physik.  Chem.  (1911),  591)  of  the 
solubilities  of  hydrogen  in  the  three  metals,  copper,  iron  and  nickel,  at  pressures  up 
to  1.5  atmospheres,  and  temperatures  from  400°  to  1600°  C.  It  is  shown  in  the  case 
of  nickel  that  the  amount  of  gas  absorbed  by  the  metal  under  given  conditions  of 
temperature  and  pressure  is  independent  of  the  amount  of  metallic  surface.  The 
hydrogen-containing  metals  are  therefore  true  solutions.  At  constant  temperature 
the  solubility  both  in  solid  and  liquid  metals  is  proportional  to  the  square  root  of 

the  gas  pressure,  the  quotient  — (where  m  is  the  mass  of  gas  absorbed  by  100  grams 

*  Berichte  (1910),  43,  893. 
Ill 


112 


THE  HYDROGENATION  OF  OILS 


a  dissolved  inlOOgr.  metal 
1 2  dissolved  In    1  gr.    ^.g 
SO 2  dlss  Jvcd  in  o'.5  gr;  Cu 


ligrams 

lligr 

[ligrams 


The  ordinate  denotes  C5  n 


900  1000  1100  1200 


1400  1500          1600       17(XTC 


THE  OCCLUSION  OF  HYDROGEN  113 

of  metal)  being  remarkably  constant  for  values  of  p  above  10  mm.  At  constant 
pressure  the  solubility  increases  with  temperature,  and  shows  a  sudden  increase  at 
the  melting  points  of  all  three  metals.  The  transition  from  ft  toy  iron  is  also  marked 
by  a  rapid  increase  in  solubility  between  850°  and  900°  C.  This  discontinuity  though 
very  marked  is  not  so  sudden  as  that  at  the  melting  point.  The  transition  from  a 
to  ft  iron  is  not  accompanied  by  any  change  in  solubility.  In  the  liquid  metals  the 
solubility  continues  to  increase  with  rise  of  temperature,  probably  more  rapidly  than 
in  the  solid  state.  On  solidifying  in  an  atmosphere  of  hydrogen  all  three  metals 
"spit."  Copper  gives  off  about  twice  its  volume  of  hydrogen  (at  1084°  C.  and 
760  mm.)  iron  about  7  times  its  volume  (at  1510°  C.  and  760  mm.)  and  nickel  about 
12  times  its  volume  (at  1450°  C.  and  760  mm.).  The  regulus  contains  cavities  in 
which  hydrogen  may  be  retained.  It  is  only,  however,  after  very  rapid  cooling  that 
any  considerable  quantity  of  the  absorbed  hydrogen  can  be  retained  at  ordinary 
temperatures. 

With  regard  to  the  occlusion  of  hydrogen  by  various  metals,  the 
following  table  is  instructive.*  The  numbers  indicate  the  volumes  of 
hydrogen  under  normal  conditions  absorbed  by  one  volume  of  the 
metal. 

Silver  wire 0.21 

Silver  powder 0 .91-0 .95 

Sheet  aluminum 1 . 1-2 . 7 

Reduced  cobalt 59-153 

Copper  wire 0.3 

Reduced  copper 0.6-4.8 

Iron  wire 0 . 46 

Cast  iron 0.57-0.8 

Reduced  iron 9 .4-19 .2 

Magnesium 1.4 

Reduced  nickel 17-18 

Gold  leaf 0.48 

Precipitated  gold 37-46 

Molten  lead 0.11-0.15 

Zinc Traces 

From  a  study  of  the  action  of  nickel  and  hydrogen  on  various  hydro- 
carbons at  different  temperatures,  the  following  conclusions  are  drawn 
by  Padoa  and  Fabrisf:  (1)  In  the  dehydrogenation  of  monocyclic 
and  polycyclic  hydrogenized  hydrocarbons,  gaseous  hydrocarbons  are 
formed  to  some  extent.  If  a  hydrocarbon  yields  several  hydro- 
genation  products,  the  most  highly  hydrogenized  one  is  most  readily 
decomposed  in  this  manner.  Of  the  hydrocarbons  examined,  tetra- 
and  di-hydrophenanthrene  yielded  no  hydrocarbon  decomposition 

*  Abegg  and  Auerbach,  Hdb.  d.  Anorganischen  Chemie  Vol.  II,  part  I,  55. 
t  J.  S.  C.  I.  (1908),  1083. 


114  THE  HYDROGENATION  OF  OILS 

products  even  under  increased  pressure,  and  tetrahydronaphthalene 
did  not  under  atmospheric  pressure. 

(2)  The  decomposing  action  of  nickel  is  influenced  by  pressure. 

For  instance,  at  atmospheric  pressure,  tetrahydronaphthalene  is 
simply  dehydrogenized  with  liberation  of  hydrogen,  whereas  under  a 
pressure  of  3  atmospheres,  gaseous  hydrocarbons  are  formed.  (3)  The 
several  hydrogenation  products  of  a  hydrocarbon  can  each  be  obtained 
from  the  most  highly  hydrogenized  product  by  the  action  of  nickel  at 
a  definite  temperature,  but  it  is  not  possible  to  effect  a  gradual  pro- 
gressive splitting  off  of  hydrogen.  In  almost  all  cases  dehydrogenation 
begins  at  a  higher  temperature  than  hydrogenation.  Under  atmos- 
pheric pressure  hydrogenation  and  dehydrogenation  are  distinct  proc- 
esses; in  most  cases  nickel  can  effect  either  reaction,  but  on  certain 
compounds,  the  nickel  acts  only  in  one  way.  Under  increased  pressure, 
the  two  limits  of  temperature,  viz.,  the  highest  at  which  hydrogenation 
is  possible  and  the  lowest  at  which  dehydrogenation  takes  place,  are 
closer  together,  and  under  certain  conditions,  the  two  processes  may 
proceed  simultaneously  until  equilibrium  is  attained. 

Relative  to  its  behavior  to  hydrogen,  Holt,  Edgar  and  Firth  *  state 
that  palladium  may  exist  either  in  an  active  or  a  passive  state,  the 
former  rapidly  taking  up  hydrogen,  the  latter  being  practically  inert. 
Heating  to  a  temperature  of  400  degrees  in  hydrogen  and  cooling 
renders  the  palladium  very  active.  New  palladium  may  be  made 
active  by  the  repeated  oxidation  and  reduction  of  the  surface.  The 
activity  diminishes  gradually  on  standing,  but  may  be  restored  on 
heating. 

When  spongy  palladium  was  exposed  to  hydrogen  at  temperatures  from  —  50°  C. 
upwards,  Gutbier  (Ber.  (1913),  1453)  found  that  the  amount  of  occluded  gas  steadily 
decreased  from  —50°  C.  (917  volumes  to  1  of  palladium)  to  a  minimum  at  20°  C. 
(661  :  1)  then  slowly  rose  to  105°  C.  (754  :  1).  The  hydrogenized  palladium  was 
pyrophoric. 

It  is  suggested  that  the  activity  is  due  to  the  presence  of  a  metastable  modifica- 
tion of  the  palladium  which  gradually  reverts  to  a  more  stable  variety  at  ordinary 
temperature.  Measurements  have  been  made  of  the  rate  of  sorption  (this  term 
includes  both  adsorption  and  absorption)  of  hydrogen  by  palladium  free  from  hydro- 
gen, and  palladium  containing  varying  amounts  of  previously-sorbed  hydrogen. 
No  marked  difference  was  observed  between  the  action  of  moist  and  dry  hydrogen. 
With  palladium  containing  little  or  no  hydrogen  the  rate  of  sorption  first  increases 
rapidly  and  then  slowly  diminishes.  On  the  other  hand,  if  the  palladium  has  al- 
ready sorbed  considerable  quantities  of  hydrogen  the  initial  increase  is  not  observed. 
It  would  appear  that  when  active  palladium  is  exposed  to  an  atmosphere  of  hydrogen 
there  is  first  a  rapid  condensation  (adsorption)  of  the  gas  at  the  surface,  probably 
in  the  form  of  complex  molecules,  forming  a  layer  of  high  vapor  pressure.  This  is 

*  Z.  physik.  Chem.,  82,  513. 


THE  OCCLUSION  OF  HYDROGEN  115 

followed  by  a  slow  diffusion  (absorption)  into  the  interior  of  the  metal.  This  would 
explain  the  rapid  rise  in  pressure  followed  by  slow  increase  observed  when  palladium 
partially  saturated  with  hydrogen  is  exposed  to  a  vacuum.  The  sorption  is  accom- 
panied by  evolution  of  heat.  Measurements  were  also  made  of  the  rate  of  diffusion 
of  hydrogen  through  a  palladium  tube.  The  rate  is  found  to  increase  with  rise  in 
temperature,  but  it  is  also  influenced  by  the  state  of  the  metal.  This  accounts  for 
the  fact  that  the  same  diffusion  velocity  is  not  always  found  at  the  same  temperature. 
It  is  very  doubtful  that  the  hydrogen  sorbed  by  the  palladium  is  at  the  same  con- 
centration throughout  the  metal,  even  after  long  standing. 

The  rate  of  absorption  of  hydrogen  by  limonene  in  the  presence  of  platinum  black 
has  been  studied  by  Vavon  (Comp.  rend.  (1914),  158,  410),  and  two  stages  or  phases 
of  the  reaction  were  noted.  The  velocity  curves  for  the  absorption  of  hydrogen 
have  a  gradient  which  varies  considerably  with  the  quantity  of  catalyst  present. 
Apparently  the  metal  can  become  fatigued  so  that  while  it  is  active  enough  to  bring 
about  the  easier  stages  of  hydrogen  addition,  it  is  not  powerful  enough  to  effect  the 
more  difficult  stages  of  saturation.  This  is  more  marked  after  the  catalyst  has  been 
heated  to  a  temperature  of  300°  C.  or  higher,  when  the  activity  can  be  varied  and 
suited  to  bring  about  hydrogenation  in  a  selective  and  regular  manner.  When 
heated  above  500°  C.  platinum  black  is  transformed  into  an  inactive  modification. 

The  work  of  Andrew  and  Holt  (Proc.  Roy.  Soc.  (1913),  A.  89,  170),  which  leads  to 
the  conclusion  that  palladium  is  dimorphic,  is  discussed  by  Halla  (Z.  physik.  Chem. 
(1914),  86,  496),  who  shows  that  palladium  black  prepared  by  Graham's  method  is 
not  inactive.  He  also  shows  that  occlusion  by  active  palladium  is  not  hindered  at 
ordinary  temperatures  by  contact  with  the  inactive  metal. 

Mixtures  of  hydrogen  and  oxygen  combine  with  explosion  on  contact  with 
platinum  or  carbon  which  has  been  heated  to  a  temperature  sufficient  to  cause 
the  emission  of  electrically-charged  particles  from  the  surfaces  of  platinum  or  carbon. 
If  platinum  is  exposed  to  Roentgen  rays  which  cause  the  emission  of  charged  par- 
ticles an  explosion  may  be  brought  about  without  heating  the  platinum.  (J.  R. 
Thompson,  Chem.  Ztg.,  Rep.  (1914),  15.) 

Investigations  directed  towards  an  explanation  of  the  precise  nature 
of  hydrogen  transfer  by  means  of  the  platinum  metals  are  not  lacking. 
Wieland*  assumes  that  palladium  hydride,  or  for  that  matter  any 
metal  hydride,  unites  as  such  with  the  unsaturated  compound  at  the 
double  bond  and  that  the  labile  addition  product  breaks  down,  with 
retention  of  the  hydrogen  and  elimination  of  palladium,  the  latter 
being  then  in  condition  to  take  up  additional  hydrogen  and  again 
form  an  addition  product.  From  a  thermodynamic  standpoint  the 
hydrogenation  process  appears  to  be  a  reversible  reaction.  In  the 
case  of  ethylene  compounds,  and  in  fact,  in  general,  the  reaction  is 
exothermic,  but  is  endothermic  in  the  case  of  the  double  bonding  of 
the  aromatic  series.  Thus  the  metal  addition  product  would  appear 
in  the  reaction  equilibrium  as  follows: 


Her.,  45,  484. 


116  THE  HYDROGENATION  OF  OILS 

In  this  connection  it  may  be  stated  that  Skita  and  associates  have 
isolated  an  addition  product  of  palladium  chloride  with  an  unsaturated 
body  but  work  along  this  line  has  not  been  extensive  and  the  explana- 
tion advanced  that  catalyzers  simply  split  the  hydrogen  molecule  to 
yield  hydrogen  in  an  atomic  or  nascent  condition  is  for  the  present 
perhaps  as  satisfactory  as  any.* 

Troost  and  Hautef euille  f  believed  that  their  experiments  vindicated 
the  formation  of  a  definite  compound  Pd2H,  while  Dewarf  suggested 
the  existence  of  PdsE^.  The  experiments  of  Hoitsema§  indicate  that 
between  20  and  200  degrees  no  definite  compounds  of  palladium  and 
hydrogen  exist. 

Sabatierll  considers  nickel  catalysis  to  be  due  to  the  formation  of 
hydrides.  First  hydrogen  acts  on  the  metal,  quickly  forming  a  com- 
pound in  the  superficial  layers  of  the  latter.  The  hydride  which  re- 
sults becomes  decomposed,  and  in  the  presence  of  bodies  which  are 
capable  of  hydrogen  addition,  union  with  the  hydrogen  takes  place. 
The  metal  is  regenerated  and  the  role  endlessly  repeated. 

The  variations  in  activity  of  nickel  which  have  been  noted  probably 
depend  on  the  formation  of  different  hydrides.  Thus,  for  example, 
well-prepared  nickel  catalyzer  may  form  the  perhydride  NiH2  which 
is  sufficiently  active  to  hydrogenate  benzol.  Nickel  prepared  at  high 
temperatures,  or  if  slightly  poisoned,  may  form  the  lower  hydride 
NiH 

1 1      which  is  not  active  on  benzol  but  which  is  catalytic  for  defines 
NiH 
and  nitro  compounds. 

Were  this  assumption  correct  it  would  appear  as  a  consequence  that 
nickel  and  the  other  active  metals  (copper,  iron,  cobalt  and  platinum) 
not  only  should  effect  a  union  of  hydrogen,  but  also  that  hydrogen- 
containing  compounds  should  suffer  removal  of  their  combined  hydro- 

*  Some  experimental  work  of  Paal  (Ber.,  45,  2221)  is  of  interest.  Paal  notes 
that  apparently  only  those  compounds  with  two  C  :  C  groups  in  which  these  groups 
are  separated  by  at  least  one  carbon  atom  can  be  catalytically  reduced  stepwise. 
Thus  PhCH  :  CHCH  :  CHAc  in  alcohol  with  colloidal  palladium  and  two  hydrogen 
equivalents  give  about  50  per  cent  each  of  the  original  ketone  and  of  the  fully  re- 
duced compound  (PhCH2)  Ac.  Similar  results  were  obtained  with  PhCH  :  CHCH  : 
C(CO2H)2,  piperinic  acid  and  piperine.  Phorone,  on  the  other  hand,  yields  almost 
quantitatively  dihydrophorone,  Me2CHCH2COCH  :  CMe2,  b.  176  degrees;  semi- 
carbazone,  needles,  m.  p.  133  to  134  degrees.  (Chem.  Abs.) 

t  Comp.  rend.,  (1874),  78,  686. 

J  Chem.  News,  (1897),  76,  274. 

§  Zeit.  phy.  Chemie  (1895),  1. 

J|  Die  Hydrierung  durch  Katalyse,  Leipsic  (1913),  17. 


THE  OCCLUSION  OF  HYDROGEN  117 

gen,  the  metals  acting  as  dehydrogenating  catalyzers.  This  actually 
proves  to  be  the  case.  Between  250°  to  300°  C.  finely-divided  copper 
readily  acts  as  a  dehydrogenating  catalyst,  converting  primary  alcohols 
to  aldehydes  and  secondary  alcohols  to  ketones,  in  fact  affording  a 
very  advantageous  method  for  bringing  about  these  transformations. 
Results  obtained  by  hydrogenation  with  nickel.  The  results  obtained 
by  hydrogenation  with  reduced  nickel  are  classed  by  Sabatier  into  4 
groups : 

1.  Simple  reduction  without  the  fixation  of  hydrogen. 

2.  Reduction  effected  simultaneously  with  the  fixation  of  hydrogen. 

3.  Fixation  of  hydrogen  by  addition  to  the  molecules  where  multiple 
bonds  exist. 

4.  Hydrogenation  effected  with  the  decomposition  of  the  molecule. 

The  well-established  impossibility  of  effecting  all  these  changes  with 
any  metal  leads  Sabatier  to  think  that  for  nickel  there  exists  many 
degrees  of  combination  with  hydrogen.  Nickel  obtained  by  the  reduc- 
tion of  the  chloride,  as  well  as  that  reduced  at  a  temperature  above 
400°  C.  is,  without  doubt,  able  to  produce  only  a  primary  hydride, 
analogous  to  that  of  copper  and  capable  of  acting  on  nitro  groups  or 
on  the  double  ethylene  bond.  Only  "  healthy  "  nickel,  such  as  that 
produced  by  the  reduction  at  a  low  temperature  of  the  oxide  obtained 
from  the  nitrate,  is  able  to  form  a  perhydride  capable  of  hydrogenating 
the  aromatic  ring. 

In  the  case  of  nickel  oxide  catalyzers  Erdmann  indicates  that  the 
transference  of  hydrogen  probably  takes  place  in  one  of  two  ways: 
either  an  intermediate  phase  represented  by  the  compounds 


HC  -  Niv  H  -  Niv 

>  O     and  > 

HC  -  Ni/  H  -  Ni/ 


or  a  decomposition  of  water  may  take  place  in  accordance  with  the 
reaction : 

Ni2O  +  H2O  =  2  NiO  +  H2 

yielding  hydrogen  in  a  nascent  state  which  is  assumed  to  unite  with 
the  unsaturated  fat  while  the  nickel  oxide  formed  is  reduced  to  the 
suboxide  by  hydrogen  in  the  molecular  condition. 

In  an  experiment  conducted  by  Mayer  and  Altmayer*  nickel, 
reduced  from  the  oxide  by  hydrogen,  was  introduced  into  a  Jena  glass 
vessel  in  an  electric  furnace,  and  after  complete  exhaustion,  known 

*  Berichte  (1908),  41,  3062. 


118  THE  HYDROGENATION   OF  OILS 

quantities  of  hydrogen  were  introduced,  and  the  temperature  kept 
constant  until  absorption  ceased.  The  amount  absorbed,  at  tempera- 
tures of  360°  to  560°  C.,  was  at  each  temperature  proportional  to 
the  pressure  of  the  hydrogen.  At  360°  C.  1  volume  of  nickel  absorbed 
50.5  volumes  of  hydrogen  at  a  pressure  of  300  mm.,  whilst  at  560°  C. 
the  same  absorption  occurred  when  the  pressure  was  raised  to  440  mm. 
Within  the  experimental  limits,  then,  the  system  nickel-hydrogen  is 
bivariant,  the  volume  absorbed  being  dependent  both  on  temperature 
and  on  pressure. 

Amorphous  palladium  absorbs  hydrogen  far  more  rapidly  than  the 
crystalline  form,  but  holds  it  only  feebly.  The  amorphous  form  also 
takes  up  hydrogen  and  transmits  it  to  the  crystalline  variety,  so  that 
crystalline  palladium  coated  with  the  amorphous  metal  will  absorb 
hydrogen  much  more  rapidly  than  when  uncoated.* 

Adsorption  is  quite  variously  regarded  by  various  authorities  as 
one  of  the  following:  (1)  True  chemical  combination.  (2)  True 
solid  solution.  (3)  A  modified  solid  solution  in  which  practically 
only  the  outer  layers  become  saturated  owing  to  the  difficulty  of  dif- 
fusion in  solids.  (4)  Condensation  on  the  outside  of  the  surface  of 
the  solid.  According  to  McBain  f  the  first  three  are  contrary  to  the 
requirements  of  thermodynamic  theory,  and  the  fundamental  assump- 
tion of  the  third  is  disproved  by  experiments  involving  the  time 
required  for  adsorption  of  hydrogen.  The  fourth  is  found  insufficient 
to  explain  the  somewhat  complex  time  relationships  studied  here,  which, 
however,  point  strikingly  to  the  conclusion  that  both  true  solid  solu- 
tion (true  diffusion)  and  surface  condensation  occur.  They  are  inde- 
pendent of  each  other  and  their  relative  importance  and  magnitude 
depend  upon  the  conditions  of  the  experiment. 

The  non-committal  name  "sorption"  is  coined  to  designate  the  sum  total  of 
the  phenomena,  while  "absorption"  and  "adsorption"  are  restricted  to  the  dis- 
solved and  superficially-condensed  matter  respectively.  It  is  found  that  the  surface 
condensation  requires  only  a  few  minutes  for  completion,  whereas  absorption  requires, 
in  the  case  of  hydrogen  diffusing  into  carbon  at  the  temperature  of  liquid  air,  a 
dozen  hours  for  practical  completion.  Thus  it  was  possible  to  isolate  the  two  phe- 
nomena and  to  study  them  more  or  less  independently  of  each  other.  For  instance, 
by  suitable  manipulation  a  sample  of  carbon  can  be  prepared  highly  charged  with 
hydrogen  in  a  state  of  solid  solution  but  almost  destitute  of  occluded  hydrogen 
condensed  on  the  surface.  This  is  clearly  attainable  (if  the  hypothesis  be  correct) 
by  suddenly  exposing  to  a  vacuum  carbon  which  has  been  previously  saturated  by 
long  contact  with  hydrogen  at  a  constant  temperature.  Such  carbon,  exposed  to  a 
low  pressure  of  hydrogen  and  cut  off  from  all  external  influences,  took  up  hydrogen 

*  Proc.  Roy.  Soc.,  London  (A),  89,  170-186,  Chem.  Abs.  (1914),  457. 
t  Seventh  Int.  Cong.  Appl.  Chem.,  1909. 


THE  OCCLUSION  OF  HYDROGEN  119 

at  first  (surface  condensation)  although  already  supersaturated  (i.e.,  in  respect  to 
the  solid  solution),  and  then  gave  it  off  again  in  still  greater  quantity  until  final 
equilibrium  was  established.  Thus  the  manometer  first  fell  for  a  few  minutes  and 
then  rose  to  a  higher  point  than  the  initial  value.  In  the  converse  case,  where  the 
interior  was  saturated  by  a  very  short  exposure  to  a  high  pressure  of  gas,  hydrogen 
was  first  given  off,  and  then  taken  up  again  by  diffusion  into  carbon.  Here  the 
manometer  automatically  rose  for  a  few  minutes,  then  steadily  fell  for  many  hours 
to  a  lower  value  than  previously  obtained.  The  pressure  changes  observed  might 
at  first  seem  unimportant,  were  it  not  for  the  one  fact  of  great  significance,  viz., 
that  (taking  the  second  case  just  outlined)  the  higher  pressure  at  five  minutes  was 
even  less  than  corresponded  to  the  gas  condensed  on  the  surface  of  the  carbon,  yet 
after  a  dozen  hours  had  elapsed  a  much  lower  pressure  was  attained,  a  pressure 
which  then  actually  did  correspond  to  the  condensed  gas  in  equilibrium  with  it. 
Thus  a  considerable  body  of  hydrogen  had  been  transferred  from  the  surface  to  the 
interior  of  the  carbon.  An  approximate  calculation  of  the  extent  of  this  transfer 
showed  that  the  true  solubility  of  hydrogen  at  the  temperature  of  liquid  air  and 
under  2  cm.  pressure  was  at  least  4  c.c.  (corr.)  per  gram  of  the  cocoanut  carbon 
employed.  This  absorption  was  roughly  proportional  to  the  square  root  of  the 
pressure  (whereas  the  total  sorption  varies  as  the  cube  root  of  the  pressure).  From 
this  it  appears  that  the  dissolved  hydrogen  is  split  up  into  single  atoms. 

Tomassi  *  considers  that  the  reductions  caused  by  hydrogen  at  the 
moment  of  its  liberation  from  its  compounds  are  wrongly  attributed 
to  its  being  in  an  allotropic  condition,!  such  as  is  usually  connoted  by 
the  term  "  nascent  ";  for,  in  that  case,  he  argues,  the  same  reactions 
ought  always  to  follow  whatever  the  origin  of  the  gas;  but  this  is  not 
borne  out  by  experiment. 

Thus,  silver  chloride,  bromide  or  iodide,  suspended  in  water  acidulated  with 
sulfuric  acid,  can  be  reduced  by  the  hydrogen  liberated  from  water  by  electrolysis, 
but  show  no  signs  of  reduction  when  the  water  is  decomposed  with  sodium  amalgam. 
Or,  if  a  solution  of  potassium  chlorate  be  acidulated  with  sulfuric  acid,  and  zinc 
added,  the  chlorate  is  reduced  to  chloride;  whereas  if  sodium  amalgam  be  added, 
no  reduction  takes  place.  Nor  does  sodium  amalgam  bring  about  the  reduction 
of  chloric  acid  or  of  the  chlorates  of  sodium,  barium,  copper,  lead  or  mercury.  In 
the  case  of  potassium  perchlorate,  none  of  the  usual  reducing  agents  have  any 
effect;  zinc  or  magnesium  with  sulfuric  acid,  or  zinc  with  potash  or  soda,  or  in  a 
boiling  solution  of  copper  sulfate,  all  failing  to  bring  about  reduction,  but,  on  the 
other  hand,  this  is  readily  effected  by  sodium  hydrosulfite  —  a  compound  from 
which  hydrogen  is  not  liberated.  Similarly,  a  solution  of  nickel  sulfate,  to  which 
potash  and  potassium  cyanide  have  been  added,  acquires  a  reddish  tint  on  the  addi- 
tion of  zinc,  while  hydrogen  is  liberated;  but  if  magnesium,  or  a  magnesium-platinum 
couple,  replace  the  zinc,  the  red  color  is  no  longer  produced,  although  hydrogen  is 
still  liberated.  Kern  found  (Bull.  Soc.  Chim.,  26,  338)  that  by  the  action  of  mag- 
nesium on  ferric  chloride,  ferric  hydroxide  was  produced,  and  this  fact  Tomassi  con- 
firms, with  the  addition  that  he  obtains  the  same  result  by  using  sodium  amalgam 

*  Monit.  Scient.,  1898  [51],  182. 

t  It  has  been  suggested  by  Osann  that  active  or  occluded  hydrogen  is  in  an 
allotropic  form  comparable  to  ozone. 


120  THE  HYDROGENATION  OF  OILS 

instead  of  magnesium.  According  to  Stahlschmidt,  nascent  hydrogen  derived  from 
the  decomposition  of  water  by  zinc  dust  reduces  potassium  nitrate  to  nitrite,  reduced 
iodides  and  iodates,  but  does  not  reduce  chlorates;  and  De  Wilde  has  established 
the  fact  that  sodium  amalgam  reduces  potassium  bromate,  but  is  without  action  on 
the  chlorate. 

On  these  and  similar  facts  Tomassi  bases  his  opinion  that  the  reducing  power  of 
nascent  hydrogen  varies  according  to  the  chemical  reaction  by  which  the  hydrogen 
was  produced,  and  he  considers  that  if  the  gas  has  a  greater  affinity  in  the  nascent 
than  in  the  ordinary  condition,  this  is  entirely  due  to  the  hydrogen  at  the  moment 
of  its  liberation  from  a  compound  being  accompanied  by  the  heat  produced  during 
the  liberation.  Hence,  if  nascent  hydrogen  be  represented  by  the  symbol  H  +  « 
(in  which  a  denotes  this  amount  of  heat),  the  value  of  a  would  vary  with  each  chem- 
ical reaction,  and,  as  a  general  rule,  the  reducing  power  of  nascent  hydrogen  would  be 
proportional  to  that  value,  provided  that  the  reaction  between  the  hydrogen  and 
the  substance  to  be  reduced  could  once  be  started.  There  are  certain  cases,  how- 
ever, in  which  the  reduction  is  due,  not  to  the  hydrogen,  but  to  the  metal  which 
served  to  generate  it.  The  reduction  of  potassium  chlorate  by  means  of  sulfuric 
acid  and  zinc,  or  by  electrolysis  of  its  solution  with  a  zinc  anode,  is  an  instance  of 
this.  If  such  a  solution  be  electrolyzed  with  both  electrodes  of  platinum,  oxidation 
occurs  at  the  anode,  with  the  formation  of  perchlorate,  while  no  trace  of  chloride 
is  found  at  the  cathode;  but  if  a  zinc  anode  be  used,  chloride  is  formed  at  the  anode, 
but  not  at  the  cathode.  From  this  Tomassi  concluded  that  the  reduction  in  this 
case  must  be  attributed,  not  to  the  hydrogen,  but  to  the  zinc  uniting  with  the  oxygen 
of  the  chlorate  in  accordance  with  the  equation  KC1O3  +  3  Zn  =  KC1  +  3  ZnO. 

Titoff  *  has  studied  the  adsorption  of  hydrogen  and  other  gases  by 
pure  gas-free  cocoanut  charcoal.  The  temperature  varied  from  —  79° 
to  +  151.5°  C.,  and  the  pressures  from  0  to  77  cm.  of  mercury.  The 
results  are  given  in  tables  and  the  relations  illustrated  by  isothermal 
and  isobaric  curves.  Hydrogen  appears  to  obey  Henry's  law  for  a 
considerable  range  of  temperature  (—  80°  to  +  80°  C.).  Titoff  pre- 
fers a  surface  condensation  theory  as  an  explanation  of  the  phenomena, 
and  consequently  he  uses  the  term  adsorption,  rather  than  absorption, 
which  would  seem  to  suggest  ordinary  solution. f 

Firth  observes  that  the  adsorption  of  hydrogen  (surface  condensation) 
by  wood  charcoal  occupies  only  a  few  minutes,  while  the  equilibrium 
due  to  absorption  is  attained  only  after  several  hours,  hence  "sorp- 
tion"  is  of  a  two-fold  character.  Wood  charcoal  contains  crystalline 
as  well  as  amorphous  carbon  and  the  activity  of  the  material  depends 
chiefly  on  the  latter.  | 

*  Z.  physik.  Chem.  (1910),  74,  641;  see  also  Homfray,  J.  S.  C.  I.  1910,  1055. 

t  Rhead  and  Wheeler  (Chem.  Soc.  Proc.  (1913),  29,  51)  observe  that  carbon,  at 
all  temperatures  up  to  900°  C.  and  probably  above  that  temperature,  has  the  power 
of  pertinaciously  retaining  oxygen.  This  oxygen  cannot  be  removed  by  exhaustion 
alone,  but  may  be  expelled  by  increasing  the  temperature  of  the  carbon  during 
exhaustion.  When  quickly  released  in  this  manner,  it  appears,  not  as  oxygen,  but 
as  carbon  dioxide  and  carbon  monoxide. 

%  Z.  physik.  Chem.  (1914),  294;  J.  S.  C.  I.  1914,  130. 


THE  OCCLUSION  OF  HYDROGEN  121 

The  presence  of  kaolin  favors  the  combination  of  hydrogen  and 
oxygen  at  temperatures  from  230  degrees  and  upwards.  Without  the 
kaolin,  combination  does  not  take  place  until  a  temperature  of  350  de- 
grees or  higher  is  reached.  The  activity  of  the  kaolin  depends  greatly 
upon  the  temperature  to  which  it  has  previously  been  heated,  and  the 
extent  to  which  it  has  lost  its  water  of  constitution.  The  lower  the 
water  content,  the  less  pronounced  is  the  activity.* 

It  has  been  stated  by  Marie  f  and  Petersenf  that,  in  the  electrolytic 
reduction  of  unsaturated  acids,  the  nature  of  the  cathode  used  has  no 
appreciable  influence  upon  the  course  and  velocity  of  the  reaction. 
Fokin§  finds,  however,  that  reduction  can  only  be  effected  with  cath- 
odes of  palladium,  platinum,  rhodium,  ruthenium,  iridium,  osmium, 
nickel  cobalt  and  copper,  and  that  the  quantity  and  the  physical 
condition  of  the  metal  has  a  considerable  influence  on  the  course  of  the 
reduction.  It  is  shown  that  the  metals  named  have  the  capacity  of 
occluding  hydrogen,  with  the  formation  of  unstable  hydrides.  It  is 
these  metals,  also,  which  have  been  found  to  act  as  hydrogen-carriers 
in  the  reduction  processes  studied  by  Sabatier  and  Senderens.  Fokin 
is  of  the  opinion  that  all  reduction  processes  taking  place  in  presence 
of  the  metals  mentioned,  viz.,  electrolytic  reduction,  reduction  of 
gaseous  substances  by  reduced  metals  by  the  process  of  Sabatier  and 
Senderens,  reduction  by  galvanic  couples,  and  reduction  by  metal 
hydrides  in  solutions,  are  due  to  a  special  activity  of  the  occluded 
hydrogen,  probably  owing  to  such  hydrogen  being  in  the  monatomic 
condition.  The  activity  of  the  metals  varies  directly  with  their 
capacity  of  occluding  hydrogen;  palladium  is  the  most  efficient,  and 
then  follow,  in  the  order  given,  platinum,  nickel,  cobalt  and  copper. 
Fokin  has  studied  in  this  way  the  reduction  of  the  fatty  acids  from 
linseed  oil,  Japanese  wood  oil,  castor  oil,  cod-liver  oil,  and  other  un- 
saturated acids. 

According  to  Fokin  the  metals  can  be  grouped  into  those  which, 
like  palladium  and  cobalt,  form  definite  hydrides;  and  those  which, 
like  platinum  and  nickel,  have  not  been  proved  to  form  such  definite 
hydrides.  The  latter  class  gives  the  best  results  in  reduction  catal- 
yses.! By  the  action  of  excess  of  cobalt  hydride  at  270°  C.,  under 
atmospheric  pressure,  oleic  acid  is  reduced  to  stearic  acid  to  the  extent 

*  J.  S.  C.  I.  1914,  254,  and  Comp.  rend.  (1914),  158,  501. 
t  Compt.  rend.,  136,  1331;  J.  S.  C.  I.  1903,  1003. 
J  Z.  Elecktrochem.,  11,  549;  J.  S.  C.  I.  1905,  895. 

§  J.  russ.  phys.  chem.  Ges.  (1906),  38,  419;  Chem.  Centr.  (1906),  2,  758;  J.  S. 
C.  I.  1906,  935. 

II  Zeitsch.  f.  ang.  Chem.  (1909),  22,  1451-1459  and  1492-1502. 


122  THE  HYDROGENATION  OF  OILS 

of  26  to  28  per  cent,  while  in  a  sealed  tube,  the  reduction  proceeds  to 
the  extent  of  60  per  cent.  If  an  ethereal  solution  of  oleic  acid  be 
treated  with  palladium  black,  and  a  current  of  hydrogen  led  through, 
stearic  acid  can  be  detected  after  one-half  hour;  with  platinum  black 
under  similar  conditions,  24  per  cent  of  stearic  acid  is  obtained  after 
one-half  hour,  84.5  per  cent  after  3J  hours  and  90  per  cent  after  5 
hours.  Oleic  acid  is  also  reduced  by  nickel  and  cobalt  (prepared  from 
the  oxides),  in  presence  of  hydrogen,  at  temperatures  of  45°  to  184°  C. 
and  98°  to  250°  C.  respectively.* 

In  order  to  test  the  view  that  the  increased  reducing  power  of 
occluded  hydrogen  is  due  to  a  kind  of  physical  compression,  Fokin 
carried  out  a  series  of  experiments,  which  showed  that  compressed 
hydrogen  (up  to  a  pressure  of  35  atmospheres)  effected  the  reduction 
of  unsaturated  hydrocarbons  more  rapidly  and  completely  and  at 
lower  temperatures  than  hydrogen  at  atmospheric  pressure. f 

Hydrogen  reduces  certain  metals  from  their  solutions,  as,  for  instance,  silver 
from  an  aqueous  solution  of  the  nitrate.  The  action  of  hydrogen  on  metallic  solu- 
tions is  much  more  energetic  when  one  operates  under  pressure  as  has  been  observed 
by  Beketoff. 

In  connection  with  the  effect  of  hydrogen  on  metallic  catalysts  to  alter  the 
properties  of  the  metal,  a  discussion  appearing  in  the  Metallurgical  and  Chemical 
Engineering  (1913),  679,  on  the  "Passivity  of  Metals,"  is  of  interest.  According 
to  Foerster  and  also  Schmidt  a  metal  such  as  iron  is  passive  in  its  normal  condition 
and  only  becomes  active  under  the  influence  of  a  catalyst.  Hydrogen  is  stated  to 
have  this  catalytic  effect  and  hydrogen  ions  have  also  the  same  action.  Schmidt 
states  that  the  most  important  of  the  catalysts  which  overcome  the  passive  state 
of  metals  is  hj'drogen  and  that  a  small  amount  of  it  can  activate  large  amounts  of 
iron,  nickel  and  chromium.  The  preparation  of  a  non-pyrophoric  catalyzer  of  the 
nickel  type  by  passing  carbon  dioxide  or  similar  gas  over  it  for  a  considerable  period 
may  perhaps  depend  on  the  elimination  of  the  hydrogen  which  permits  the  metal 
to  resume  its  normal  passive  state,  in  which  condition  exposure  to  the  air  does  not 
injure  the  catalytic  activity. 

Towards  hydrogen,  palladium  in  sheet  form  appears  to  be  both 
active  and  passive.  In  the  active  form  the  metal  will  rapidly  absorb 
large  amounts  of  the  gas,  while  in  the  passive  condition  only  slight 
amounts  are  occluded.  The  absorption  of  hydrogen  proceeds  in  two 
stages;  first,  a  rapid  occlusion  at  the  surface  and  second,  a  slow  ab- 
sorption into  the  metal  mass.J: 

*  J.  S.  C.  I.  1907,  1149. 

t  J.  S.  C.  I.  1907,  169. 

t  Zeitsch.  phys.  Chem.  (1913),  513. 


CHAPTER  VIII 
THE  ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS* 

The  hydrogenation  of  oils  has  to  such  an  extent  changed  certain  of 
the  constants  by  which  oils  and  fats  are  at  least  in  part  identified, 
namely,  the  iodine  number  and  the  specific  gravity,  that  the  identifi- 
cation of  a  fat  or  fatty  mixtures,  often  heretofore  a  troublesome  matter 
at  best,  now  promises  to  become  even  more  difficult. 

The  reduction  of  the  iodine  number  through  the  introduction  of 
hydrogen  into  the  oil,  in  a  sense,  is  arbitrary ;  there  is  no  difficulty  in 
reducing  the  iodine  number  almost  to  zero  through  the  hydrogenation 
process,  or  at  any  moment  to  interrupt  the  operation  and  from  one  and 
the  same  initial  material  to  produce  products  having  the  most  varied 
iodine  numbers. 

The  specific  gravity  and  melting  point  advance  hand  in  hand  as 
saturation  progresses,  the  specific  gravity  approaching  that  of  tri- 
stearin,  while  the  resultant  melting  point  in  considerable  measure  de- 
pends upon  the  molecular  weight  and  the  hydroxyl  content  of  the 
fatty  acid  components  of  the  oil.  The  specific  gravity  of  a  hardened 
cottonseed  oil  whose  iodine  number  had  been  reduced  to  zero  was 
found  by  Normann  and  Hugel  f  to  be  0.9999  at  15°  C.,  while  they  note 
that  tristearin  has  a  specific  gravity  of  1.0101  at  the  same  temper- 
ature.t 

The  index  of  refraction  also  is  strongly  modified.  A  sample  of  fish 
oil  at  56°  C.,  according  to  Normann  and  Hugel,  showed  a  figure  of 
53.8;  while  after  hardening  to  an  iodine  number  of  22.5  the  index  was 
36°  C.  at  the  same  temperature.  (Scale  of  the  Zeiss  butter  refrac- 
tometer.) 

Observations  made  in  the  author's  laboratory  on  the  index  of  re- 
fraction of  a  number  of  hydrogenated  oils  gave  the  results  noted 
below :  § 

*  Jour.  Ind.  Eng.  Chem.  (1914),  117. 

t  Chem.  Ztg.  (1913),  815. 

t  The  specific  gravity  of  tristearin  is  given  by  the  Chemiker  Kalender  as  1.0101 
at  15°  C.,  while  Lewkowitsch  reports  the  specific  gravity  of  a  specimen  of  not  quite 
pure  stearin  in  the  melted  state  as  0.9235  at  65.5°  C. 

§  A  sample  of  hydrogenated  cottonseed  oil  used  extensively  in  this  country 
exhibited  a  refractive  index  of  1.4492  and  a  melting  point  of  59.9°  C. 

123 


124 


THE  HYDROGENATION  OF  OILS 


INDEX  OF  REFRACTION  AT  55°  C. 

(Abb6  Refractometer  *) 


Original  oil 

Hydrogenated  oil 

Corn 

1  4615 

4514  (M  P  55  7°  C  ) 

Whale  (No.  1) 

1  4603 

4550  (M.  P  41  5°  C  ) 

Soya  bean. 

1  4617 

.4538  (M.  P.  50.3°  C.) 

Cocoanut  oil  ("olein") 

1.4429 

.4425  (M.  P.  24  7°  C.) 

Linseed  

1.4730 

.4610  (M.  P.  42.3°  C.) 

Palm  

1.4523 

.4517  (M.  P.  38.7°  C.) 

Pal  in 

1  4523 

4494  (M   P  44  8°  C  ) 

Peanut  (edible)  

1.4567 

1.4547  (M.  P.  34.7PC.) 

It  is  of  interest  to  note  that  while  the  addition  of  hydrogen  to  fatty 
oils  reduces  the  index  of  refraction,  the  addition  of  oxygen  increases  the 
index  as  is  shown  in  the  case  of  blown  or  ozonized  oils. 

The  gradual  reduction  of  the  index  of  refraction  by  progressive 
hydrogenation  is  shown  in  the  following  table  compiled  from  deter- 
minations made  in  the  author's  laboratory. 

Cottonseed  oil  was  hydrogenated  for  a  period  of  ten  hours  and 
samples  were  drawn  at  one-hour  intervals. 


Melting  point 

Index  of  refraction, 
55°  C. 

Original  oil   . 

4588 

1  hour  

28  2°  C 

4577 

2  hours  

31  3 

4568 

3  hours  

34  3 

4557 

4  hours 

37  9 

4549 

5  hours 

40  8 

4540 

6  hours 

43  8 

4527 

7  hours  

45  6 

4518 

8  hours  

47  3 

4510 

10  hours  

55  9 

4496 

The  saponification  number  practically  does  not  change.  The  con- 
tent of  free  fatty  acids  changes  but  little.  A  sample  of  cottonseed  oil 
containing  1.8  per  cent  fatty  acid  was  found,  after  hardening  to 
various  degrees,  to  have  a  fatty  acid  content  ranging  from  1.4  per  cent 
to  1.9  per  cent.  With  sesame  oil  containing  2.44  per  cent  fatty  acid 
the  resulting  hardened  oil  contained  2.55  per  cent  of  acid.  The  con- 
tent of  unsaponifiable  bodies  does  not  essentially  change.  Cotton- 
seed oil  having  0.55  per  cent  unsaponifiable  matter,  after  hardening, 

*  Refraction  values  are  given  in  terms  of  true  refractive  index  and  also  according 
to  the  arbitrary  scale  of  the  butyro  refractometer,  in  order  to  follow  the  data  avail- 
able, as  rendered. 


ANALYTICAL  CONSTANTS  OF  HYDROGEN ATED  OILS     125 


showed  a  content  of  unsaponifiable  bodies  ranging  from  0.45  per  cent 
to  0.55  per  cent;  sesame  oil  with  an  unsaponifiable  content  of  0.70 
per  cent,  after  hardening,  contained  0.85  per  cent  unsaponifiable. 

Cholesterol  and  phytosterol,  according  to  Bomer,  are  not  changed 
by  treating  oils  with  hydrogen,  although  this  is  somewhat  contrary 
to  the  statement  of  Windaus,*  according  to  whom  cholesterol  may  be 
easily  reduced  by  the  catalytic  process.  Willstatter  and  Mayer  f 
hydrogenated  cholesterol  in  ether  solution  with  a  platinum  catalyzer. 

An  examination  of  the  unsaponifiable  constituents  of  several  hardened 
oils  has  been  made  by  Marcusson  and  Meyerheimt  who  used  the  digi- 
tonin  method  for  the  separation  of  sterol.  The  following  table  gives 
the  results  obtained. 

UNSAPONIFIABLE  CONSTITUENTS  OF  HARDENED  OILS 


- 

Total 
unsap- 
onifi- 
able 
matter 

Sterol 
obtained 
by  digi- 
tonin 
method 

Sterol-free  unsaponifiable 
components 

Per 

cent 

H> 

Per 

cent 

Per 
cent 

MD 

Iodine 
number 

Cottonseed  oil  (solidifying  point  32°  C.) 
Cottonseed  oil  (solidifying  point  38°  C.) 
Linseed  oil 

0.7 
0.6 
1.0 
0.3 
0.9 
0.9 
0.8 
0.7 

-  5.8 
±  0 
+  19.5 
-10.1 
-  1.9 
-  3.3 
+  4.7 
+  1-4 

0.22 
0.14 
0.21 
0.13 
0.10 
0.07 
0.05 
0.024 

0.4 
0.4 
0.7 
0.19 
0.7 
0.7 
0.7 
0.64 

+  6.8 
+  8.1 
+19 
+  5.2 
+  1.3 

+  'i!8 
+  2.8 

85" 
56.  i 

Castor  oil 

Talgol 

Talgol  extra. 

Candelite 

Candelite  extra. 

The  examination  showed  that  the  sterol  content  of  hardened  fats  is 
slightly  less  than  that  of  the  corresponding  natural  fat  or  oil.  The 
cottonseed  oil  first  listed  was  prepared  by  the  Wilbuschewitsch  process 
at  150  to  160°  C.  with  hydrogen  under  pressure.  The  second  sample 
of  the  cottonseed  oil  was  made  by  the  Normann  process,  presumably 
at  a  higher  temperature  but  without  pressure.  At  temperatures  of 
150  to  160°  C.  apparently  the  difficultly  reducible  sterol  is  not  affected 
by  hydrogen  and  Marcusson  and  Meyerheim  call  attention  to  the 
observations  of  Adamla  §  who  could  not  hydrogenate  cholesterol  with  a 

*  Ber.  d.  chem.  Ges.  (1912),  3051. 

t  Willstatter  and  Mayer  converted  cholesterol  quantitatively  into  dihydro- 
cholesterol  by  passing  a  slow  stream  of  hydrogen  for  two  days  through  an  ethereal 
solution  of  cholesterol  in  the  presence  of  platinum  black  (Ber.,  1908  (41),  2199). 
(See  U.  S.  Patent  to  Ellis,  1,086,357,  Feb.  10,  1914.) 

t  Zeitsch.  f.  angew.  Chem.,  1914;  28,  201. 

§  Dissertation.     Beitrage  zur  Kenntnis  des  Cholesterins,  Freiburg,  1911,  12. 


126 


THE  HYDROGENATION  OF  OILS 


nickel  catalyzer  at  temperatures  below  170°  C.  Marcusson  and  Meyer- 
heim  found  cholesterol  to  hydrogenate  readily  at  195°  C.  while  phytos- 
terol  was  practically  unchanged  after  treatment  with  hydrogen  at 
200°  C.  From  these  and  other  tests  it  was  found  that  cholesterol  is 
much  less  resistant  than  phytosterol  to  the  action  of  hydrogen. 

The  content  of  sterol  decreases  with  increasing  melting  point  as  shown 
by  the  following  table. 


Hydrogenated  oil 

Iodine 
number 

Solidifying 
point 

Sterol 
content 

Whale  oil  (not  hydrogenated)  
Talgol  

114 

67 

31 

0.13 
0.10 

Talgol  extra 

36 

38 

0  07 

Candelite 

20 

42 

0  05 

Candelite  extra  

13 

45 

0.02 

The  unsaponifiable  constituents  of  hardened  fat  when  freed  from 
sterols  were  of  light  yellow  color  and  of  salve-like  consistency.  These 
sterol-free  bodies  obtained  from  Talgol,  Talgol  extra,  Candelite  and 
Candelite  extra,  when  recrystallized  from  benzine,  yielded  a  product 
melting  between  59.3°  and  59.8°,  which  proved  to  be  a  fatty  alcohol, 
probably  octodecyl  alcohol.. 

In  the  case  of  the  acetyl  number  more  noticeable  changes  take  place 
according  to  Normann  and  Hugel.  When  hardening  castor  oil,  for 
example,  the  hydroxyl  number  in  one  sample  dropped  from  156  to  102; 
in  another  sample  the  number  fell  to  131.  The  hydroxyl  group  is  thus 
more  or  less  broken  down  by  the  hydrogenation  process,  at  least  under 
some  conditions  of  treatment. 

HYDROGENATED   CASTOR  OIL 

Acid  number 3.5 

Saponification  number 183 . 5 

Iodine  number 4.8 

Acetyl  number 153 . 5 

Acetyl  number  of  the  fatty  acids 143 .1 

Acid  number  of  the  fatty  acids '. 184 . 5 

Saponification  number  of  the  fatty  acids 187.9 

Melting  point  of  the  fat 68°  C. 

Melting  point  of  the  fatty  acids 70°  C. 

Melting  point  of  the  acetylated  acids 47°  C. 

The  properties  of  hardened  castor  oil  have  been  noted  by  Garth* 
whose  observations  differ  somewhat  from  those  of  Normann  and 
Hugel.     As  is  generally  known,  castor  oil  differs  materially  from  many 
*  Seifen.  Ztg.  (1912),  1309. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS     127 

other  common  oils  in  such  respects  as  its  high  viscosity,  solubility  in 
alcohol  and  difficulty  of  salting  out  its  soaps  by  electrolytes.  Hard- 
ened castor  oil  dissolves  in  alcohol  only  by  heating  and  separates  on 
cooling,  but  is  soluble  at  ordinary  temperature  in  chloroform.  The 
constants  of  one  sample  of  hardened  castor  oil  examined  by  Garth  are 
given  in  the  above  table. 

These  results  obtained  by  Garth  would  indicate  that  the  saponifi- 
cation  and  acetyl  number  do  not  change.  The  iodine  number  has 
fallen  greatly  and  the  melting  point  is  much  increased.  The  differ- 
ence between  the  acid  number  of  the  fatty  acids  and  their  saponifica- 
tion  number  points  to  the  formation  of  lactones.  As  is  known  castor 
oil  has  the  property  at  high  temperatures  of  forming  anhydrides, 
accompanied  by  polymerization. 

The  effect  of  hydrogenation  on  color  tests  of  oils  is  variable.  Thus 
the  Boudouin  sesame  oil  test  is  not  influenced;  in  fact  the  reaction 
seemingly  is  sharper  after  treatment  of  the  oil  with  hydrogen,  while 
the  Halphen  test  is  not  likely  to  give  positive  results  even  with  oils 
which  have  been  only  slightly  hardened. 

The  Becci  test  is  operative  with  slightly-hardened  cottonseed  oil, 
but  is  indistinct  with  highly-hardened  oil  so  that  this  test  is  significant 
only  in  event  of  a  positive  coloration. 

Hardened  fish  oil  loses  all  its  essential  characteristics,  such  as  the 
formation  of  well-defined  bromine  compounds  of  the  higher  unsatu- 
rated  fatty  acids.  Thus  there  are  obtained  after  hardening,  new  fatty 
acids  corresponding  to  the  saturated  bodies,  arachidic  (C2oH4002)  and 
behenic  (C^^Cy  acids,  which  in  variable  amounts  up  to  a  proportion 
of  20  per  cent  and  more  have  been  observed  in  certain  hydrogenated 
oils.  In  the  hardening  of  rape  oil  behenic  acid  is  formed  from  the 
erucic  acid  present.  Other  oils  or  fats  with  a  noticeable  proportion  of 
acids  with  more  than  18  carbon  atoms  in  the  molecule  apparently 
scarcely  ever  come  into  the  trade. 

The  complete  conversion  of  erucic  acid  to  behenic  acid  is  readily 
obtained  by  reducing  with  hydrogen  in  the  presence  of  nickel.  This 
method  has  been  used  by  Lewkowitsch  in  the  determination  of  erucic 
acid.* 

The  saturated  fatty  acids  obtained  by  the  hydrogenation  of  the  un- 
saturated  acids  of  Japanese  sardine  oil  were  found  by  Majima  and 
Okada  f  to  have  a  melting  point  of  75°  C.  and  a  molecular  weight  of 
349,  and  consisted  in  the  main  of  the  higher  homologues  of  stearic 
acid,  such  as  C2oH4oO2  or  C^H^C^.  Similar  results  were  obtained  on 

*  Lewkowitsch,  Oils,  Fats  and  Waxes,  5th  edition,  Vol.  I,  195  and  553. 
t  J.  S.  C.  I.,  1914,  362. 


128  THE  HYDROGENATION  OF  OILS 

hydrogenating  the  more  fluid  fatty  acids  obtained  by  chilling  and 
pressing. 

As  a  test  for  hydrogenated  peanut  oil,  Kreiss  and  Roth*  have  given 
a  method  which  consists  in  saponifying  20  grams  of  the  oil  with  40  cc. 
of  alcoholic  potash;  then  adding  60  cc.  of  alcohol  and  acidifying  by 
the  addition  of  50  per  cent  acetic  acid  of  which  approximately  15  cc. 
are  required.  One  and  one-half  grams  of  lead  acetate  are  added  and 
the  mixture  allowed  to  stand  overnight.  The  lead  salts  which  sepa- 
rate are  decomposed  by  boiling  with  5  per  cent  hydrochloric  acid,  the 
fatty  acids  are  dissolved  in  50  cc.  of  90  per  cent  alcohol  with  slight 
warming  and  the  solution  is  placed  in  water  at  15  degrees  for  about 
one-half  hour.  The  crystals  which  separate  are  recrystallized  from 
25  cc.,  then  12J  cc.  of  90  per  cent  alcohol  and  the  melting  point  deter- 
mined. The  presence  of  at  least  5  per  cent  arachidic  acid  causes  the 
melting  point  of  the  third  crystallization  to  be  over  70°  C. 

Normann  and  Hugelf  state  that  this  test  is  applicable  likewise  to 
hardened  fish  and  rape  oil.  They  tested  a  number  of  samples  of  fish 
oil  from  several  sources  and  found  in  each  case  that  the  melting  point 
of  the  recrystallized  fatty  acids  was  at  least  70  degrees.  Normann  and 
Hugel  also  state  that  it  is  unnecessary  with  hardened  fish  oil  to  allow 
the  lead  acetate  to  react  for  several  hours,  it  sufficing  simply  to  let  the 
mixture  stand  until  cooled  to  room  temperature;  this  can  be  hastened 
by  cooling  with  water.  So  large  a  proportion  of  fatty  acids  is  obtained 
according  to  this  procedure  that  the  specified  amount  of  alcohol  is  not 
sufficient  to  dissolve  them.  It  is  better  to  use  100  to  150  cc.  of  alcohol 
and  heat  on  the  water  bath  until  solution  is  affected.  The  application 
of  heat  should  not  be  continued  for  any  great  length  of  time  as  arachidic 
acid  readily  forms  esters.  The  mixture  is  then  placed  in  cold  water, 
cooled  to  room  temperature  and  the  separated  material  collected  and 
crystallized  several  times  from  alcohol  used  in  progressively  diminish- 
ing proportions.  Three  crystallizations  suffice  for  only  slightly  hard- 
ened fats.  With  fats  of  higher  consistency  one  must  recrystallize 
several  times  more  until  the  melting  point  is  constant. 

In  one  case  using  hardened  fish  oil  having  a  melting  point  of  44, 
three  recrystallizations  from  alcohol  gave  a  constant  melting  point  of 
only  63  degrees,  while  further  recrystallization  using  acetone  caused 
the  melting  point  to  advance  to  76  degrees.  In  doubtful  cases  one 
should  try  several  solvent  mediums.  If  the  melting  point  is  found  to 
be  above  70°  C.  Normann  and  Hugel  think  it  proof  that  either  hard- 
ened fish,  rape  or  peanut  oil  is  present.  If  one  is  certain  of  the  unitary 

*  Chem.  Ztg.  (1913),  58  and  369. 
t  Ibid.  (1913),  815. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS     129 


character  of  the  oil  then  peanut  and  rape  oil  can  be  distinguished  from 
fish  oil  by  the  cholesterol  test,  provided  the  statement  of  Bomer  in 
regard  to  the  unchangeability  of  cholesterol  and  phytosterol  under 
ordinary  conditions  of  oil  hydrogenation  is  confirmed. 

Data  on  hardened  oils  by  Davidsohn*  are  tabulated  below: 


M.  P. 

Acid 
number 

Saponifi- 
cation 
number 

Moisture 

Ash 

Talgol 

39  3 

3  4 

191   0 

0  10 

0  07 

Talgol  extra 

46  5 

3  5 

191  3 

0  13 

0  05 

Candelite 

49  0 

3  2 

191  0 

0  20 

0  08 

Candelite  extra. 

51.9 

3  9 

190  8 

0  15 

0  04 

Coryphol  .    .        .           ?  . 

79.3 

3.3 

189.9 

0  18 

0  05 

These  hardened  fish  oils  or  other  hardened  oils  put  out  under  the 
trade  names  indicated  are  manufactured  by  the  Germania  Oil  Works 
of  Emmerich. 

Knappf  states  that  the  attention  of  analysts  should  be  directed  to 
the  fact  that  in  the  immediate  future  they  will  be  called  upon  to  ana- 
lyze certain  new  artificial  fats  prepared  by  hydrogenation  and,  not 
improbably,  to  detect  their  presence  as  adulterants.  Thus,  for  ex- 
ample, starting  with  olive  oil,  as  the  absorption  of  hydrogen  proceeds, 
a  turbid  oil,  then  a  liquid  magma,  then  a  soft  fat  and  finally  a  hard 
fat  is  obtained.  Knapp  observes,  "  A  similar  change  occurs  with  all 
oils  containing  glycerides  of  unsaturated  acids.  This  rise  in  the  melt- 
ing point  is  naturally  accompanied  by  a  decrease  in  the  iodine  value 
and  refractive  index.  Fats  have  been  prepared  in  this  way  from  cot- 
tonseed oil  with  iodine  values  as  low  as  5,  and  if  desired  the  iodine 
value  could  doubtless  be  reduced  to  0,  and  the  melting  point  raised  to 
60°  or  70°  C.  While  it  is  too  costly  for  commercial  purposes  to  carry 
the  saturation  of  the  unsaturated  glycerides  to  completion,  it  might 
be  of  value  in  the  laboratory  as  an  aid  to  determining  the  component 
glycerides  in  a  pure  oil.  Not  only  the  oils  containing  glycerides  of 
oleic  acid  can  be  hardened,  but  also  those  containing  glycerides  of 
linolic  acid  and  linoleic  acid  (the  drying  oils),  and  even  of  such  highly 
unsaturated  acids  as  clupanodonic  (in  whale  oils).  Anyone  who  has 
seen  a  malodorous  oil  converted  into  a  bland  odorless  tallow  realizes 
the  commercial  possibilities  of  the  process.  And  when  it  is  remem- 
bered that  the  process  can  be  stopped  when  the  iodine  value  reaches 
a  desired  number,  the  possibility  becomes  evident  of  the  preparation 

*  Org.  f.  d.  Ol-und  Fetthdl.  (1913),  Nos.  14  and  15,  and  Seifen.  Ztg.  (1913),  529. 
t  The  Analyst  (1913),  102. 


130 


THE  HYDROGENATION  OF  OILS 


of  a  fat  with  any  required  analytical  figures.' 
going,  Knapp  furnishes  the  following  data: 


In  support  of  the  fore- 


Hardened  oils 

Appearance 

Clear  liquid 

Solid  particles 
floating 

Soft  greasy 
solid 

Brittle  solid 

Butyro-refractometer    (cor- 
rected to  40°  C  ) 

57  7 

47  7 

Fatty  acids: 
Iodine  value 

110 

94 

55 

22 

Titer 

34.  7°  C. 

37.0°  C. 

42  5°  C. 

52  2°  C. 

Neutralization  value: 
(mg.  KOH)  

197 

196 

196 

192 

The  analyst  is  chiefly  interested  in  the  question  of  how  these  fats 
are  to  be  detected.  It  is  doubtful  if  their  most  characteristic  feature, 
the  relatively  high  percentage  of  stearic  glycerides  which  they  contain, 
will  be  of  much  service.  Knapp  states  that  until  the  manufacturer 
accomplishes  the  difficult  step  of  completely  removing  the  nickel,  the 
detection  of  traces  of  this  metal  will  be  the  simplest  and  most  reliable 
test  for  hardened  oils.*  Although  the  catalyst  is  very  finely  divided, 
the  manufacturer  can  obtain  a  perfectly  clear  fat  by  careful  filtration, 
and  hence  it  is  the  nickel  contained  in  the  nickel  soaps  formed  by  the 
free  fatty  acids  present  that  one  has  to  detect.  The  following  method 
is  suggested :  50  grams  of  the  fat  are  heated  in  a  flask  with  20  cc.  hydro- 
chloric acid,  with  continued  vigorous  shaking.  The  mixture  is  allowed 
to  separate  while  hot,  and  part  of  the  acid  solution  is  evaporated  to 
dryness,  dissolved  in  a  drop  of  water  and  placed  on  a  white  tile.  One 
drop  of  ammonium  sulfide  is  added  to  this  and  also  to  a  drop  of  water 
for  comparison.  Knapp,  however,  tried  this  test  only  on  a  few  hard- 
ened oils,  and  in  some  cases  with  negative  results.  Dimethylglyoxime 
is  a  much  more  delicate  test,  but  unfortunately  Prall  has  found  f  that 
certain  pure  untreated  oils  give  a  red  coloration.  Hence  further 
investigation  is  needed. 

One  of  the  most  characteristic  tests  for  fish  oils  —  the  bromide 
estimation  —  is  quantitatively  useless  for  these  oils  after  hardening, 

*  Too  much  reliance  should  not  be  placed  on  the  nickel  test  as  evidencing  the 
presence  or  absence  of  hydrogenated  oils.  It  is  known  to  the  writer  that  hardened 
oils  which  are  free  from  nickel  are  on  the  market,  these  in  some  cases  presumably 
having  been  prepared  with  the  aid  of  palladium  as  a  catalyzer. 

t  Bonier,  Zeitsch.  Untersuch.  Nahr.  Genussn,  (1912),  24,  104,  and  Analyst  (1912), 
37,  452. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS     131 


as  the  percentage  of  ether-insoluble  brominated  glycerides  is  greatly 
reduced  thereby.  Not  only  are  the  analytical  figures  for  the  oils 
altered  by  this  absorption  of  hydrogen,  but  also  the  traces  of  substances 
which  often  serve  as  a  useful  test  for  the  particular  oil  in  which  they 
occur  —  e.g.,  Halphen's  reaction.  Knapp  believes  Bomer's  observa- 
tion that  phytosterol  and  cholesterol  are  not  changed  in  this  process 
is  of  great  analytical  value. 

Three  fats  obtained  by  Knapp  from  a  clear  cottonseed  oil,  hardened 
by  hydrogen  with  the  help  of  different  catalysts,  gave  the  following 
figures : 


Catalyst 

Percentage  of 
catalyst 

Character  of 
product 

Butyro-refrac- 
tion 
(Corrected  to 
40°  C.) 

Melting  point, 
°C. 

Nickel  

1   00 

Hard 

45  7 

49 

Platinum  

1    10 

Hard 

47  8 

46 

Palladium  

0  06 

Brittle 

45  5 

52 

The  keeping  properties  of  these  hardened  oils  were  found  to  be 
remarkably  good.  Although  prepared  nearly  a  year  and  a  half  pre- 
viously and  having  often  been  exposed  to  damp  air,  yet  they  showed 
no  signs  of  rancidity.  The  free  acidity  (0.70  per  cent  as  oleic  acid) 
did  not  appreciably  change  during  the  period  of  observation. 

Bomer*  is  in  substantial  agreement  with  the  foregoing,  for  he  states 
that  (1)  the  hardened  oils,  as  a  result  of  the  more  or  less  complete 
transformation  of  unsaturated  fatty  acids  (oleic,  linoleic,  linolenic) 
into  stearic  acid,  show  an  increase  in  the  melting  and  solidifying  points 
as  well  as  a  lowering  of  the  refractometer  number  and  iodine  number 
while  the  saponification  number  is  but  little  altered. 

(2)  Judging  by  the  iodine  numbers  of  the  liquid  fatty  acids,  these 
acids  appear  to  be  not  uniformly  transformed  into  stearic  acid,  but 
the  transformation  of  oleic  acid  appears  to  progress  more  slowly  than 
the  less  saturated  linoieic  and  linolenic  acids,  etc.f 

(3)  Among  the  hardened  oils,  the  soft  and  medium-hard  products, 
in  color,  consistency  and  in  part  also  in  odor  and  taste  show  a  greater 
or  less  similarity  to  beef  or  mutton  tallow,  so  that  by  external  appear- 

*  Chem.  Rev.  u.  d.  Fett  und  Harz  Ind.  (1912),  220. 

t  Muller  (Seifen.  Ztg.  (1913),  1376)  examined  a  hydrogenated  fish  or  whale  oil 
known  as  Talgit,  having  an  iodine  number  of  49,  and  found  the  iodine  number  of 
the  liquid  fatty  acids  obtained  from  this  material  to  be  100,  from  which  he  concludes 
that  the  addition  of  hydrogen  occurs  simultaneously  with  both  the  oleic  and  the 
more  unsaturated  acids  and  not  successively  in  such  a  manner  as  to  convert  the 
acids  containing  two  or  more  double  bonds  into  oleic  acid  before  oleic  becomes 
transformed  into  stearic  acid. 


132 


THE  HYDROGENATION  OF  OILS 


ance  one  cannot  distinguish  these  hardened  oils  from  such  animal 
fats;  for  example  medium-hard  peanut  oil  is  so  completely  like  neutral 
lard,  and  hardened  whale  oil  is  so  like  mutton  tallow,  that  one  is  not 
able  to  distinguish  between  these  fats  by  appearance,  consistency, 
odor  or  taste. 

(4)  Not  only  in  their  outward  properties  are  these  hardened  oils 
like  hog  fat  and  mutton  tallow,  but  also  the  usual  analytical  constants 
are  so  similar  that  one  cannot  distinguish  some  samples  of  hardened 
peanut  oils  and  hardened  sesame  oil  from  hog  fat,  nor  whale  oil,  in 
some  cases,  from  mutton  or  beef  tallow.  In  the  latter  case  even  the 
Polenske  numbers  agree  while  in  the  case  of  sesame  oil  they  are  some- 
what lower  than  hog  fat. 


Oil 

Appearance 

Melt- 
ing 
point 

Solidi- 
fying 
point 

Refrac- 
tometer 
at  40° 

Acid 

No.* 

Saponi- 
fication 
No. 

Iodine 
No. 

Peanut  oil  un- 
treated. 

Yellow  liquid 

56  8 

1    1 

191  1 

84  4 

Peanut  oil 
hardened 

White  tallowy  .  .  . 

51.2 

36.5 

50.1 

1.0 

188.7 

47.4 

Sesame  oil 
hardened 

White  tallowy  .  .  . 

62.1 

45.3 

38.  4t 

4.7 

188.9 

25.4 

Cottonseed  oil 
hardened 

Yellowish 
lard  like 

38  5 

25  4 

53  8 

0  6 

195  7 

69  7 

Cocoanut  oil  un- 
treated 

White  soft 

25  6 

20.4 

37.4 

0.3 

255  6 

11  8 

Cocoanut  oil 
hardened 

White  lard  like.  .  . 

44.5 

27.7 

35.9 

0.4 

254.1 

1.0 

Whale  oil  hardened.. 

Yellowish  tallowy 

45.4 

33.7 

49.1 

1.1 

193.0 

46.8 

Milligrams  potassium  hydroxide  for  1  gram  fat. 


t  Determined  at  50°  C. 


Bomer  examined  a  number  of  hydrogenated  oils  and  tabulated  the 
results  of  his  investigations  and  from  these  the  above  condensed  table 
has  been  compiled. 

The  solid  and  liquid  fatty  acids  separated  from  the  hydrogenated 
fat  by  the  method  of  Farnsteiner  showed  the  following  properties: 


Oil 

Solid  fatty  acids 

Liquid  fatty  acids 

M.  P. 

Acid  No. 

Refraction  at 
40°  C. 

Iodine 
No. 

Peanut  oil  untreated  

47.6 
42.9 
44.7 
48.3 
44.4 

91.8 

82.9 
88.9 
115.6 
96.0 

Peanut  oil  hardened 

199.7 
199.5 
206.8 
199.5 

Sesame  oil  hardened 

56.4 
45.0 

Cottonseed  oil  hardened  ....       ... 

Whale  oil  hardened  

ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS     133 

Samples  of  these  hardened  oils  were  examined  for  cholesterol  and 
phytosterol.  Hardened  peanut  oil  was  found  to  contain  0.4  per  cent, 
sesame  oil  1.9  per  cent,  cottonseed  oil  1.6  per  cent  and  whale  oil  0.2 
per  cent  of  sterol,  of  which  the  three  first-mentioned  hardened  products 
exhibited  the  typical  crystalline  form  of  phytosterol.  The  melting 
point  of  these  sterols  ranged  from  132°  to  139°  C.,  yielding  acetates 
melting  between  about  126°  and  129°  C.  The  hardened  whale  oil  gave 
a  sterol  melting  at  149.7°  C. 

Bomer  made  a  series  of  fractional  crystallizations  of  hardened  oil 
and  from  a  sample  of  hydrogenated  peanut  oil  obtained  tristearin 
(amounting  to  about  f  per  cent).  Bomer  has  called  attention  to  the 
rather  striking  behavior  of  cocoanut  oil.  He  calculated  from  the 
iodine  number  that  the  natural  oil  contained  13  per  cent  of  oleic  acid 
and  after  hydrogenation  approximately  about  1  per  cent  of  this  acid 
was  present.  As  a  result  of  the  transformation  of  12  per  cent  of  oleic 
acid  into  stearic  acid,  the  melting  point  increased  from  25.6°  to  44.5°  C., 
or  thus  18.9°  C.,  while  the  solidifying  point  advanced  from  20.4°  to 
27.7°  C.,  or  only  7.3°  C. 

Bomer*  has  studied  the  melting  points  of  hydrogenated  oils  and  as 
regards  hydrogenated  peanut  and  sesame  oil  he  notes  that  the  melting 
points  of  the  least  soluble  glycerides  are  very  high,  being  70.6°  C.  and 
71.5°  C.  respectively,  while  the  corresponding  fatty  acids  melted  at 
68.6°  C.  and  68. 5°  C.;  hence  these  glycerides  apparently  consist  of 
tristearin.  The  hydrogenated  cottonseed  oil  examined  yielded  a  mix- 
ture of  glycerides  of  melting  point  61.3°  C.  and  derived  fatty  acids 
melting  at  38°  C. 

A  species  of  hardened  fish  or  whale  oil,  known  as  "Talgit,"  has  been 
examined  by  Mullerf  who  found  the  product  to  have  an  acid  value  of 
12.8,  an  iodine  number  of  49  and  a  titer  (fatty  acids)  of  39.4°  C.  The 
fat  was  saponified  and  pressed  to  obtain  stearic  acid.  It  was  found 
that  the  operation  of  pressing  could  be  carried  out  effectively  to  yield 
a  product  technically  free  from  liquid  fatty  acids;  35  per  cent  of  solid 
fatty  acid  having  a  titer  of  48.7°  C.  was  thus  obtained.  Miiller  states 
that  since  mixtures  of  stearic  and  palmitic  acids  possess  a  solidifying 
point  above  53.5°  C.  the  low  titer  of  the  solid  acids  of  Talgit  points  to 
the  presence  of  solid  acids  other  than  stearic  and  palmitic.  DubovitzJ 
thinks  the  low  melting  point  to  be  due  to  the  presence  in  the  original 
fish  or  whale  oil  of  hypogaeic  and  physetoleic  acid  or  similar  acids  with 
possibly  unsaturated  fatty  acids  of  a  still  lower  number  of  carbon  atoms. 

*  Z.  Untersuch.  Nahr.  Genussm.  1914,  153;  J.  S.  C.  I.,  1914,  323. 
t  Seifen.  Ztg.  (1913),  1376. 
t  Ibid.  (1913),  1445. 


134 


THE  HYDROGENATION  OF  OILS 


Leimdorf er  *  regards  the  stearin  produced  by  the  hydrogenation 
of  some  oils  to  be  perhaps  an  allotropic  form  of  natural  stearin. 

The  hydrogenation  of  linseed,  peanut  and  sesame  oil,  using  nickel 
oxide  as  a  catalyzer,  according  to  Bedford  and  Erdmann,  affords 
approximately  pure  stearic  glyceride.f 

An  attempt  is  made  by  Grimme  t  to  identify  fish  oils  after  they 
have  been  hardened.  As  stated,  the  ordinary  constants  give  no  clue 
to  the  original  source  of  a  hardened  oil  and  hence  Grimme  resorts  to 
color  reactions.  A  list  of  tests  is  given  for  each  of  the  four  classes  of 
fish  oils:  (1)  Seal  oils;  (2)  Whale  oils;  (3)  Liver  oils;  (4)  Fish  oils; 
and  also  characteristic  tests  for  individual  oils.  These  tests  were  also 
applied  to  two  hardened  oils  of  unknown  origin  and  Grimme  believes 
from  his  results  that  the  color  reactions  are  characteristic  enough  to 
establish  the  presence  of  fish  oils.  Nickel  was  found  in  the  samples, 
Fortini's  test  (as  detailed  below)  giving  the  strongest  coloration. 
Color  reactions  were  applied  to  six  authentic  whale  oils  from  two  dif- 
ferent sources,  and  hardened  to  different  degrees.  These  tests  were 
carried  out  by  dissolving  5  parts  of  the  sample  in  95  parts  of  benzine- 
xylene  (1:1)  and  agitating  5  cc.  of  the  solution  with  the  reagent; 
after  5  minutes  and  60  minutes  the  color  was  noted.  Grimme  finds 
the  iodine-sulfuric  acid  reaction  (1  cc.  concentrated  sulfuric  acid  and 
1  drop  tincture  of  iodine)  to  give  a  characteristic  violet-red  color  for 
whale  oil  though  the  intensity  of  coloration  decreases  with  increasing 
hardness.  '  The  constants  of  the  six  samples  of  hydrogenated  fish  and 
whale  oils  employed  and  the  coloration  produced  by  different  reagents 
are  tabulated  by  Grimme. 


CONSTANTS  OF  HYDROGENATED  FISH  AND  WHALE  OILS 


Sample 

Consistency 

Specific 
gravity 

Melt- 
ing 
point 

Solidi- 
fying 
point 

Index 
of  re- 
fraction 

Acid 
No. 

Acid 
No.  aa 
free 
oleic 
acid,  % 

Saponi- 
fication 
No. 

Iodine 
No. 

(Wijs) 

I 

Lard  like 

0  9256 

°C. 

38  5 

°C. 

32  8 

1  4569 

3  72 

i  01 

ICC    Q 

PJ6    7A 

II  

Tallowy 

0  9259 

40  0 

35  2 

1  4548 

8  49 

4  26 

189  8 

40  Qo 

Ill  

Tallowy  . 

0  9258 

42  4 

36  4 

1  4543 

5  64 

2  90 

189  6 

41  36 

IV 

Tallowy 

0  9263 

44  8 

39  3 

1    4AQQ 

4  3Q 

0    01 

1QQ    0 

QC  71 

v   . 

Tallowy 

0  9271 

47  2 

41  5 

1  4536 

4  40 

2  25 

1QQ    7 

2fi  Q1! 

VI  

Tallowy 

0  9271 

48  0 

42  0 

1  4530 

2  18 

1  10 

IRQ  3 

OQ    1C 

*  Ibid.  (1913),  1317. 

f  Jour.  f.  prakt.  Chem.,  1913,  432. 

t  Chem.  Rev.  u.  d.  Fett  und  Harz  Ind.  (1913),  129  and  155. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS     135 


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136  THE  HYDROGENATION  OF  OILS 

A  draft  of  the  Codex  alimentarius  Austriacus,  which  has  been  pre- 
pared by  a  board  of  prominent  chemists  and  officials  including  Hefter, 
Wolfbauer,  Fischer,  Hartl  and  Pellischek,*  embraces  the  subject  of 
hydrogenated  oils  and  it  is  stated  that  considered  as  a  food  product 
these  oils  will  require  further  careful  investigation  before  it  is  deter- 
mined with  certainty  just  what  rank  they  will  take  as  edible  products. 
It  is  noted  that  the  fats  now  offered  for  edible  purposes  are  white  to 
yellowish  in  color,  almost  odorless  and  tasteless.  Usually  the  con- 
sistency lies  between  that  of  ordinary  butter  and  hard  tallow.  Now 
and  then  samples  are  found  which  melt  at  about  60°  C.  and  are  as 
brittle  as  carnauba  wax.  These  hard  products,  of  course,  are  not 
intended  by  themselves  to  be  used  for  edible  purposes,  but  are  em- 
ployed to  raise  the  melting  point  of  soft  fats.  Samples  of  hardened 
peanut  and  sesame  oil  with  iodine  numbers  reduced  to  50  or  lower, 
sometimes  down  to  20,  have  been  examined.  Cocoanut  oil  with  an 
iodine  number  of  2  or  even  lower  has  been  met  with.  The  cholesterol 
of  animal  fats  and  the  phytosterol  of  vegetable  oils  are  not  altered  by 
the  hydrogenation  process.  The  hardened  fats,  it  is  stated,  scarcely 
ever  appear  on  the  market  in  their  true  light,  but  usually  are  put  out 
under  some  trade  name  such  as  "  Peanut-oleo,"  "  Sesame-oleo," 
"  Peanut-margarine/'  "  Sesame-margarine/'  "  Crisca,"  and  the  like. 

Hardened  oils  examined  by  Aufrechtf  in  outward  appearances 
resembled  palm  kernel  oil.  They  were  very  hard  and  of  granular 
fracture,  were  either  pure  white  or  yellowish  in  color.  A  distant  odor 
was  perceptible  on  melting  or  heating.  The  taste  recalled  that  of 
tallowy  fats.  The  products  were  readily  soluble  in  the  usual  fat 
solvent  mediums,  but  the  solubility  in  methyl  and  ethyl  alcohol  was 
very  slight.  The  fats  were  easily  saponifiable.  The  content  of  free 
fatty  acid  fluctuated  between  0.51  to  0.83  per  cent.  The  ash  reacted 
alkaline  and  consisted  of  alkali  carbonate  and  traces  of  iron  oxide,  but 
no  nickel  or  other  constituent  could  be  detected.  The  analytical 
results  are  given  in  table  on  the  following  page. 

The  detection  of  traces  of  nickel  by  the  usual  analytical  methods  is 
often  difficult 4  Dimethylglyoxime,  proposed  by  Tchugaeff,  is  a 
reagent  of  great  sensitiveness.  Its  application  has  been  investigated 
by  a  number  of  chemists,  and  among  these  Bianchi  and  Di  Nola§ 
report  that  the  presence  of  copper  and  iron  interferes  with  the  test. 
They  worked  with  an  acid  reagent  and  used  the  following  procedure: 

*  Seifen.  Ztg.  (1913),  1087. 
t  Pharm.  Ztg.  (1912),  876. 

J  Methods  of  determination  are  given  by  Grossmann,  Die  Bestimmungmethoden 
des  Nickels  und  Kobalts,  Stuttgart,  1913. 
§  Boll.  Chim.  Farm.  (1910),  517. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS     137 


To  the  substance  supposed  to  contain  nickel  one  or  two  drops  of 
concentrated  hydrochloric  or  nitric  acid  are  added  and  the  acid  solu- 
tion so  obtained  is  placed  in  a  porcelain  dish,  or  preferably  on  a  strip 
of  filter  paper.  A  few  drops  of  ammonia  are  added,  or  in  case  the 
strip  of  filter  paper  is  used,  this  may  simply  be  exposed  to  the  vapors 
of  ammonia.  The  liquid  is  acidified  with  acetic  acid  and  a  drop  of 
concentrated  alcoholic  solution  of  dimethylgloxime  is  added.  The 
presence  of  nickel  is  shown  by  a  red  coloration  which  grows  more  pro- 
nounced in  the  course  of  time.  This  reaction  is  a  very  simple  one  and 
does  not  require  any  particular  technical  knowledge  for  carrying  out. 


1 

Durotol 
(yellow) 

-  2 
Durotol 
(white) 

3 
Hydrogen- 
ated  train  oil 

Color 

Yellowish. 

White 

Whifp 

Specific  gravity  at  15°  C  

0  9252 

0  9257 

0  9268 

Melting  point,  °C 

46  5 

46  0 

48  0 

Solidification  point,  °C 

43  5 

43  5 

45  5 

Viscosity  at  50°  C. 

5  4 

5  4 

5  6 

Acid  No.  (calculated  as  oleic  acid)  
Saponification  No. 

0.51 
162  2 

0.57 
161  0 

0.83 
173  5 

Unsaponifiable  matter  (per  cent) 

1  92 

2  1 

2  4 

Acetyl  No 

1  2 

1  2 

0  95 

Iodine  No. 

3  9 

4  2 

7  8 

Hehner  No. 

95  8 

95  § 

96  4 

Reichert-Meissl  No. 

0  38 

0  36 

0  52 

Water  

0  0 

0  0 

0  0 

Ash  

0  037 

0  03 

0  05 

Fortini  *  has  simplified  this  reaction  and  uses  an  alkaline  instead  of 
an  acid  reagent  which  apparently  gives  more  satisfactory  results  than 
the  above  procedure.  Fortini  mixes  one-half  gram  of  dimethyl- 
glyoxime,  5  cc.  98  per  cent  alcohol,  and  5  cc.  concentrated  ammonium 
hydroxide  in  the  order  given,  yielding  a  clear,  faintly  yellowish  liquid 
which  in  glass-stoppered  bottles  may  be  kept  for  a  long  time  unchanged. 
The  test  is  carried  out  as  follows: 

The  sample  to  be  examined  is  freed  from  fat  by  extraction  with 
ether  and  to  the  residue  a  drop  of  the  reagent  is  added.  When  nickel 
is  present  there  will  appear  in  a  few  seconds  a  rose-colored  flock  caused 
by  reaction  with  the  nickel  oxide  present  on  the  surface  of  the  metallic 
nickel.  Of  course,  if  nickel  is  present  in  the  form  of  a  soap,  the  fat 
should  be  extracted  with,  for  example,  aqueous  hydrochloric  acid  in 
the  manner  prescribed  by  Knapp  in  the  foregoing.  In  order  to  make 
the  reaction  even  more  sensitive,  the  residue  may  be  heated  for  a  few 
moments  in  an  oxidizing  flame  to  produce  nickel  oxide. 
*  Chem.  Ztg.  (1912),  1461. 


138  THE  HYDROGENATION  OF  OILS 

Kerr*  proposes  the  following  modification  of  the  dimethylglyoxime 
test  for  nickel  in  hydrogenated  oils  and  fats: 

Ten  grams  of  the  fat  to  be  tested  are  heated  on  the  steam  bath  with 
10  cc.  of  hydrochloric  acid  (specific  gravity  1.12),  with  frequent  shaking 
for  2  to  3  hours.  The  fat  is  then  removed  by  filtering  through  a  wet 
filter  paper,  the  filtrate  being  received  in  a  white  porcelain  dish.  The 
filtrate  is  evaporated  to  dryness  on  the  steam  bath,  2  to  3  cc.  of  concen- 
trated nitric  acid  being  added,  after  it  has  been  partly  evaporated,  to 
insure  the  destruction  of  all  organic  matter.  After  the  evaporation  is 
complete  the  residue  is  dissolved  in  a  few  cubic  centimeters  of  distilled 
water  and  a  few  drops  of  a  one  per  cent  solution  of  dimethylglyoxime  in 
alcohol  added.  A  few  drops  of  dilute  ammonia  are  then  added.  The 
presence  of  nickel  is  shown  by  the  appearance  of  the  red  colored  nickel 
dimethylglyoxime.  The  amount  of  nickel  present  may  be  estimated 
by  comparing  the  color  developed  with  that  developed  in  a  standard 
solution  of  a  nickel  salt. 

The  detection  and  determination  of  small  quantities  of  nickel  by 
a-benzildioxime  is  described  by  Atack  f  as  follows : 

An  alcoholic  solution  of  a-benzildioxime  gives  with  nickel  compounds 
a  bulky  red  precipitate  which  is  insoluble  in  water,  alcohol,  acetone, 
10  per  cent  acetic  acid  and  ammonia;  the  precipitate  becomes  reddish 
yellow  on  boiling.  The  reagent  is  much  more  sensitive  than  dimethyl- 
glyoxime, showing  1  part  of  nickel  in  5  million  of  water,  and  the  pre- 
cipitate is  readily  filtered,  t  Small  quantities  of  nickel  are  determined 
as  follows:  150  cc.  of  a  hot  saturated  alcoholic  solution  of  the  oxime 
are  added  for  every  0.01  gram  of  nickel,  the  mixture  is  heated  for 
a  few  minutes  on  the  water  bath,  filtered,  the  precipitate  washed 
with  hot  alcohol,  and  dried  at  110°  to  112°C.;  it  has  the  formula 
C28H22N404NI  and  contains  10.93  per  cent  Ni.  Nickel  may  be  sepa- 
rated from  cobalt  in  ammoniacal  solution.  a-Benzildioxime  is  pre- 
pared by  boiling  10  grams  of  benzil,  dissolved  in  50  cc.  of  methyl 
alcohol,  with  a  concentrated  aqueous  solution  of  8  grams  of  hydroxyl- 
amine  hydrochloride,  for  6  hours,  washing  the  precipitate  with  hot 
water  and  then  with  a  small  quantity  of  ethyl  alcohol,  in  which  it  is 
only  slightly  soluble.  It  may  be  crystallized  from  acetone. 

According  to  Lindt,  nickel  may  be  determined  colorimetrically  by 
means  of  potassium  thio carbonate.  Metals  of  the  hydrogen  sulfide 
group  and  manganese,  cobalt  and  zinc  should  not  be  present.§ 

*  Jour.  Ind.  &  Eng.  Chem.,  1914,  207. 

t  Chem.  Ztg.  (1913),  37,  773. 

J  Compare  Ibbotson,  J.  S.  C.  I.  (1911),  1317. 

§  J.  S.  C.  I.,  1914,  335. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS     139 

The  hydrogen  value  is  proposed  by  Fokin*  as  a  means  of  deter- 
mining unsaturated  organic  compounds  in  a  manner  similar  to  the 
iodine  values  of  Hubl  and  Wijs. 

The  "  hydrogen  value  "  of  an  organic  compound  is  defined  as  the 
number  of  cubic  centimeters  of  hydrogen  (at  0  degrees  and  760  mm.), 
which  are  absorbed  by  1  gram  of  the  compound.  For  the  test  an 
apparatus  is  devised  consisting  of  a  distillation  flask  (50  to  150  cc.) 
having  a  small  beaker  fused  inside  on  the  bottom,  and  connected  by 
means  of  the  side  tube  to  a  gas  burette  and  a  gasometer  containing 
hydrogen.  In  the  small  beaker  are  placed  about  0.1  gram  of  catalytic 
platinum,  moistened  with  J  cc.  of  water,  and  in  the  flask  the  substance 
to  be  examined  and  20  to  30  cc.  of  alcohol  free  from  dissolved  oxygen. 
Hydrogen  is  admitted  and  the  flask  is  shaken  by  a  shaking  machine 
until  absorption  is  complete.  The  following  hydrogen  values  were 
obtained  by  Fokin,  the  figures  in  parentheses  being  either  the  hydrogen 
values  corresponding  with  Wijs'  iodine  value,  or,  where  indicated,  the 
theoretical  hydrogen  values.  Elaidic  acid,  78.6  to  81.4  (78.8);  oleic 
acid,  86.2  to  87.2  (86.2);  fatty  acids  from  sunflower  oil,  119.6  to  120.8 
(122.9);  fatty  acids  from  linseed  oil,  164.9  to  166.3  (166.0);  castor  oil, 
73.7  (75.5);  croton  oil,  260.9  (theoretical,  258.4);  undecoic  acid, 
115.6  (114.1);  erucic  acid,  39.4  (65.6).  Colophony  does  not  absorb 
hydrogen  under  the  conditions  of  the  test.  The  "  hydrogen  value  " 
of  course  is  not  a  determination  as  yet  of  use  in  the  identification  of 
hardened  oils,  but  is  noted  here  because  of  its  incidental  interest. 

The  foregoing  embraces  most  of  the  information  available  from 
published  sources  on  the  analytical  side  of  hydrogenated  or  hardened 
oils  and  it  is  hoped  that  the  very  meagerness  of  the  data  may  serve  as 
a  stimulus  for  abundant  investigations  tending  to  clarify  the  subject 
and  enabling  fairly  definite  procedures  to  be  adopted  for  the  qualita- 
tive and  quantitative  examination  of  these  products. 

*  J.  Russ.  Phys.  Chem.  Soc.,  40  (1908),  700;  J.  Chem.  Soc.  Abstr.,  94  (1908), 
II,  637. 


CHAPTER   IX 
EDIBLE   HYDROGENATED   OILS 

Since  the  addition  of  less  than  1  per  cent  of  hydrogen  suffices  to 
convert  cottonseed  oil  or  other  vegetable  oils  into  a  fatty  body  of 
at  least  the  consistency  of  lard,  it  follows  that  manufacturers  of 
ordinary  lard  compound  (that  is  to  say,  a  mixture  of  about  85  to 
90  per  cent  of  refined  cottonseed  oil  and  10  to  15  per  cent  or  so  of 
oleo-stearin)  have  promptly  turned  their  attention  to  the  production 
of  compound  by  a  "  self-thickened  "  cottonseed  oil. 

The  high  cost  *  of  oleo-stearin  prevailing  during  recent  years  makes 
the  method  an  attractive  one  and  the  hydrogenated  product  from 
cottonseed  oil  has  the  advantage,  if  properly  made,  of  being  very 
stable  in  character.  Unquestionably,  also,  the  hardening  process  is 
destined  to  increase  the  demand  for  cottonseed  oil  in  the  manufacture 
of  edible  fats. 

By  the  hydrogenation  process  a  lard  substitute  may  be  prepared 
in  two  ways.  The  entire  oil  may  be  simply  hardened  to  the  consis- 
tency of  lard,  care  being  taken  to  employ  an  oil  as  nearly  neutral 
as  possible  to  prevent  excessive  solution  of  catalytic  metal,  and  to 
avoid  a  high  temperature  of  treatment  so  as  not  to  impair  the  flavor 
of  the  product.  If  the  color  and  flavor  are  detrimentally  affected, 
resort  may  be  had  to  a  further  treatment  with  fuller's  earth  followed 
by  steam-vacuum  deodorization.  The  addition  of  a  small  amount 
of  cocoanut  oil  benefits  the  flavor. 

The  other  method  is  that  of  making  lard  compound  which,  as  indi- 
cated above,  involves  thickening  a  large  proportion  of  normal  oil 
with  a  small  amount  of  a  relatively-hard  hydrogenated  product. 
This  may  be  carried  out  as  follows: 

After  the  oil  has  been  hardened,  it  is  freed  of  catalyzer  and  then 
may  be  run  into  tanks  containing  the  requisite  amount  of  deodorized 
cotton  oil  (or  other  edible  oil)  and  if  necessary  the  mixture  is  further 
clarified  and  filter-pressed.  With  hardened  cotton  oil  of  58  to  60 

*  Even  though  there  may  exist  no  marked  price  differential  between  oleo-stearin 
and  hardened  cottonseed  oil,  yet  when,  as  is  the  case,  millions  of  pounds  of  lard 
compound  are  made  weekly  in  this  country,  a  reduction  in  cost  of  but  a  small  frac- 
tion of  a  cent  per  pound  means  an  important  gross  saving. 

140 


EDIBLE  HYDROGENATED  OILS 


141. 


liter,  only  7  to  10  per  cent  is  required  to  thicken  the  oil  to  the  con- 
sistency of  lard,  although  in  hot  climates  a  somewhat  larger  propor- 
tion may  be  needed.*  The  mixture  is  run  onto  a  chill  roll  to  cause 
rapid  solidification  and  after  slight  aeration  to  improve  the  color 


FIG.  51. 


is  ready  to  be  packaged.     Fig.  51  shows  a  chill  roll  or  lard  cooler  of 
the  type  usually  employed. 

In  this  illustration  the  large  upper  cylinder  or  roll  is  chilled  by  the 
circulation  of  brine  and  is  slowly  rotated  say  from  6  to  10  r.p.m. 
The  hot  liquid  compound  at  a  temperature  of  50°  to  55°  C.  is  run 
into  the  feeding  trough  7  and  falls  onto  the  chilling  roll,  forming 
a  thin  somewhat  translucent  film  which  quickly  cools  and  solidifies. 
The  solid  fat  is  removed  by  a  scraper  and  falls  into  a  picker  trough  5. 
The  latter  contains  a  shaft  equipped  with  beating  and  conveying 
blades  which  churn  the  composition  and  destroy  the  translucency,  pro- 
ducing an  opaque  white  product  of  lard-like  appearance.  The  picker 
is  run  at  a  relatively  high  speed,  say  175  to  180  r.p.m.  Fig.  52  is 
an  end  view  showing  chill  roll,  feeding  trough  and  picker.  Fig.  53 
is  an  illustration  of  a  modified  type  of  compound  cooler.  In  Fig.  54 
the  cooler  and  picker  appear  on  the  left  hand  and  in  the  center  is  a  pump 
which  withdraws  the  product  from  the  picker  and  forces  it  through 
the  pipe  line  to  the  packaging  cocks  on  the  right  hand.  Too  high  a 

*  The  main  object  to  be  achieved  in  making  edible  and  lard  compounds  is  to 
have  them  contain  as  large  a  percentage  of  cottonseed  oil  as  possible  and  yet  fulfil 
the  required  conditions  as  to  the  stiffness  of  the  material  to  withstand  warm  temper- 
atures without  much  softening.  Compound  which  stands  a  moderately  warm  climate 
can  be  made  with  even  as  low  as  6  to  7  per  cent  hardened  oil. 


142  THE  HYDROGENATION  OF  OILS 

speed  of  the  picker  blades  incorporates  an  excessive  amount  of  air 
in  the  product  rendering  it  "fluffy."* 

The  speed  of  rotation  of  the  chilling  roll  is  governed  by  the  rate  of 
feed  and  temperature  of  the  brine.  The  latter  may  be  kept  between, 
for  example,  —5  to  +10°  F.  for  good  results.  If  the  brine  is  too 
cold,  the  product  is  liable  to  drop  badly  from  the  roll  and  the  texture 


END   VIEW. 

FIG.  52. 

is  not  always  satisfactory.  This,  however,  may  be  largely  remedied 
by  increasing  the  feed.  In  winter  the  brine  may  be  held  at  a  slightly 
higher  temperature  to  prevent  brittleness.  In  the  hottest  weather, 
very  cold  brine  should  be  used  to  aid  in  securing  a  product  which  will 
preserve  its  color  and  consistency  for  a  considerable  time. 

When  properly  made  the  compound  derived  by  the  hydrogenated 
oil  thickener  is  excellent  in  color,  texture,  flavor  and  keeping  qual- 
ities. By  many  it  is  considered  superior  in  several  respects  to  oleo- 
stearin  compound. 

*  The  author  desires  to  make  acknowledgment  to  the  Allbright-Nell  Co.  of 
Chicago  and  the  Brecht  Co.  of  St.  Louis  for  their  courtesy  in  furnishing  the  illustra- 
tions Figs.  51  to  54. 


EDIBLE  HYDROGENATED  OILS 


143 


Possibly,  however,  for  best  results  as  to  stability  it  is  desirable  to 
hydrogenate  the  entire  body  of  oil  to  a  fatty  acid  titer  of  36  or  38, 
or  whatever  consistency  may  be  required,  rather  than  to  take  a  rela- 
tively small  proportion  of  the  oil  and  harden  it  to  a  titer  of  50  to  60 


FIG.  53. 


or  thereabouts  and  incorporate  with  unhydrogenated  oil.  It  appears 
that  the  hydrogenation  of  the  total  body  of  the  oil,  by  transforming 
the  linoleic  and  linolenic  compounds  and  the  like,  has  a  tendency  to 
improve  the  oil  as  regards  its  edibility  and  certainly  gives  it  greater 
stability.  The  flavor  of  lard  compound  is,  however,  preferred  by 


FIG.  54. 

many  large  users  of  lard  substitute  presumably  because  of  the  pro- 
portion of  normal  oil  which  it  contains,  and  the  manufacturing  cost 
is  lower. 

Finally,  it  may  be  stated,  by  partial  saturation  of  glycerides,  we 
have  the  possibility  of  preparing  from  tri-olein  the   oleo-distearin 


144  THE  HYDROGENATION  OF  OILS 

or  the  dioleostearin.  Dioleopalmitin  would  give  either  oleostearo- 
palmitin  or  distearopalmitin.  From  tri-olein  we  may  have  the  two 
isomeric  oleo-distearins,  a-  and  /3-oleo-distearin  as  well  as  a-  and 
iS-dioleostearin.  Which  of  these  we  may  be  able  to  produce  control- 
lably  and  which  may  prove  best  from  the  edible  standpoint  are  problems 
for  the  future  to  solve. 

Joslin*  calls  attention  to  the  economy  in  using  hardened  oil  "  vege- 
table stearin"  in  place  of  oleo-stearin  for  making  lard  compound, 
since  only  7  to  10  per  cent  of  the  former  is  called  for  against  14  to 
20  per  cent  of  the  oleo-stearin.  Of  course  the  amount  of  hardened 
oil  required  depends  on  its  degree  of  "  hardness  "  but  for  the  present 
grades  of  hydrogenated  cottonseed  oil  of  58  to  60  titer,  now  on 
the  market,  the  above  proportions  hold.  When  the  oil  is  hardened  to 
about  the  consistency  of  average  oleo-stearin,  naturally  a  greater  pro- 
portion is  needed  in  lard  compound. 

Joslin  notes  the  resultant  economy  by  the  employment  of  hardened 
oil  at  one  plant  during  a  period  of  one  year. 

93  parts  cottonseed  oil  at  6.45.  . $6.00 

7  parts  hardened  oil  (vegetable  stearin)  at  9.25 .65 

Cost  per  hundred  pounds  of  compound $6 . 65 

86  parts  cottonseed  oil  at  6.45 $5 . 55 

14  parts  oleo-stearin  at  9.25 1.29 

Cost  per  hundred  pounds  of  compound $6 . 84 

Or  a  saving  of  practically  20  cents  per  hundred  pounds  of  compound 
manufactured. 

Hydrolecithin  has  been  prepared  from  lecithin  by  Riedel.f  A  hard- 
ened fat  called  "Brebesol"  intended  for  edible  purposes  is  manufac- 
tured by  the  Bremen  Besigheimer  Olfabriken.J 


EDIBILITY  OF  HYDROGENATED  OILS 

It  seems  to  be  generally  accepted  by  those  who  have  investigated 
the  matter  carefully  that  the  hydrogenated  oils  have  as  desirable  a 
degree  of  edibility  as  the  oils  from  which  they  are  derived.  It  is  even 
claimed  that  by  destroying  traces  of  certain  unsaturated  bodies 
thought  to  be  slightly  toxic  in  nature,  hydrogenation  renders  the  oil 
better  adapted  for  human  consumption. 

*  National  Provisioner  1914,  17. 

t  Method  of  Preparing  Hydrolecithin.     German  Patent.     Compare  Paal  and 
Oehme,  Ber.,  1913,  1297. 
t  Seifen.  Ztg.,  1914,  263. 


EDIBLE  HYDROGENATED  OILS  145 

A  question  of  serious  import  has,  however,  arisen  in  the  use  of 
nickel  catalyzer.  Aside  from  the  fact  that  by  careless  filtration 
traces  of  the  suspended  nickel  may  be  present  in  the  product,  there 
is  the  more  serious  problem  of  the  actual  solution  of  nickel  to  form 
nickel  soaps  which  cannot  be  easily  removed. 

According  to  Bomer,*  nickel  is  dissolved  by  oils  during  the  hydro- 
genation  treatment  only  when  the  oil  contains  free  fatty  acid  in 
considerable  amounts.  A  sample  of  hydrogenated  sesame  oil  con- 
taining 2J  per  cent  of  fatty  acid  was  found  to  contain  0.01  per  cent 
ash  with  0.006  per  cent  nickel  oxide.  Whale  oil,  containing  0.6  per 
cent  fatty  acid,  yielded  0.006  per  cent  ash  and  0.0045  per  cent  nickel 
oxide.  Such  an  amount  of  nickel  possibly  would  be  regarded  as  unde- 
sirable or  objectionable  in  a  product  intended  for  edible  purposes. f 

*  Zeitsch.  Nahr.  Genussm.  (1912),  104  and  Chem.  Rev.  u.  d.  Fett.  u.  Harz.  Ind. 
(1912),  221. 

f  In  a  discussion  of  Bomer's  paper  (loc.  cit.)  Lehmann  asked  whether  nickel 
was  found  in  sufficient  amounts  to  make  a  quantitative  determination  in  hydro- 
genated oils,  and  Bomer  replied  that  the  amount  of  nickel  was  just  so  much  larger 
the  greater  the  amount  of  free  acid  in  the  oil  and  the  longer  the  action  of  the  catalyzer 
on  the  oil;  while  Prall  observed  that  the  nickel  content  of  hardened  oil  depended 
essentially  upon  the  amount  of  free  acid  and  that  one  should  reduce  the  free  fatty 
acid  to  the  lowest  possible  amount,  that  with  0.2  per  cent  free  fatty  acid  in  the  oil 
no  nickel  had  been  detected  in  the  hardened  products  examined.  One  could  say, 
however,  that  in  100  grams  of  oil  a  fraction  of  a  milligram  of  nickel  is  detected. 
Lehmann  then  remarked  that  presumably  it  was  to  be  understood  that  the  presence 
of  nickel  could  not  be  avoided  and  that  one-half  a  milligram  of  nickel  in  100  grams 
of  the  oil  would  be  a  good  result,  to  which  Prall  replied  that  this  was  the  case  when 
the  acid  of  the  oil  was  well  removed. 

Auerbach  (Chem.  Ztg.,  37,  297)  regards  the  0.000002  per  cent  or  so  of  nickel 
which  remains  in  hydrogenated  oil  to  be  of  no  practical  moment  from  the  stand- 
point of  edibility. 

An  oil  mill  in  Europe  making  high-grade  peanut  oil  is  now  constructing  a  plant 
for  hardening  edible  oils  by  a  hydrogenation  process  that  is  said  to  afford  a  product 
free  from  the  objectionable  traces  of  nickel  found  in  most  of  these  oils.  The  hardened 
oil  will  be  sold  to  the  margarine  factories. 

Lehmann  stated  (Bomer,  loc.  cit.)  that  we  need  have  no  great  concern  over  the 
utility  of  this  fat  or  of  its  physiological  action;  Straub  noted  that  samples  of  the 
hardened  oiMbielted  at  53°  C.  and  that  fats  of  such  high  melting  point  or  in  fact  any 
fat  melting  above  37°  C.  were  not  suitable  for  persons  affected  with  certain  maladies 
of  the  digestive  tract.  Lehmann  remarked  that  the  work  carried  on  in  the  Voit  labo- 
ratory indicated  high  melting  point  fats  to  be  injurious,  but  considering  the  way 
hardened  fats  are  made,  apparently  the  means  were  at  hand  to  make  the  melting 
point  high  or  low  at  will;  that  fats  which  were  to  be  eaten  must  not,  of  course,  have 
a  melting  point  of  53°  C.  Bomer  added  that  he  was  of  the  opinion  that  hardened 
fats  were  not  as  beneficial  as  oil,  but  that  was  not  the  question.  The  widespread 
use  of  edible  oils  depended  on  the  fact  that  edible  fats  must  have  a  certain  measure 
of  consistency.  Margarine  melting  at  20  degrees  required  but  a  slight  addition  of 


146  THE  HYDROGENATION  OF  OILS 

The  use  of  nickel  in  the  form  of  an  oxide,  or  the  use  of  nickel  catalyzer 
containing  a  considerable  proportion  of  oxide,  is  perhaps  undesirable 
from  the  point  of  view  of  solubility  in  oil.  Nickel,  in  the  metallic 
state,  cannot  combine  with  a  fatty  acid  to  produce  a  soap,  except 
with  the  elimination  of  hydrogen,  and  in  the  presence  of  an  atmosphere 
wholly  of  hydrogen,  because  of  mass  action,  such  reaction  would  not 
be  likely  to  take  place.  On  the  other  hand,  nickel  in  the  form  of 
oxide  would  yield  water  on  combining  with  fatty  acid  which  would  be 
yielded  practically  into  a  vacuum  as  regards  the  vapor  pressure  of 
water.  Hence  in  the  manufacture  of  products  intended  for  edible 
purposes  it  is  suggested  that  conditions  be  maintained  such  that  the 
catalyzer,  if  of  the  nickel  type,  is  preserved  almost  wholly  in  the 
metallic  state.  Also  it  is  desirable  to  not  force  the  reaction  too 
rapidly  with  the  consequent  danger  of  breaking  down  the  carboxyl 
group  and  setting  free  water  which  would  react  to  produce  fatty  acid.* 

a  fat  melting  at  50  degrees.  It  was  not,  therefore,  a  question  of  the  melting  point 
of  the  hardened  oil,  but  of  the  melting  point  of  the  margarine  or  other  edible  fat 
and  the  hardened  oil  was  employed  simply  to  adjust  the  melting  point,  the  same  way 
as  beef  tallow  and  the  like  were  used. 

A  synopsis  of  Bomer's  paper  (Z.  Nahr.  Genussm.,  24,  104^113)  appearing  in 
Chemical  Abstracts,  Nov.  10,  1912,  3201,  concisely  expresses  his  work.  Samples 
of  peanut,  sesame,  cottonseed  and  whale  oil  were  hardened.  The  analyses  of  the 
resulting  products  indicate  that  the  more  completely  unsaturated  fatty  acids  (oleic, 
linolenic  and  linoleic)  are  converted  into  stearic  with  increase  in  the  melting  point 
and  the  lowering  of  the  iodine  number,  while  the  saponification  number  is  scarcely 
altered.  The  iodine  number  of  the  liquid  acids  seems  to  indicate  that  the  less  satu- 
rated acids  are  more  rapidly  converted  into  stearic  than  is  oleic.  The  partially 
saturated  products  resemble  lard  in  color,  taste  and  odor,  while  those  obtained  by 
further  hardening  are  very  similar  to  beef  or  mutton  tallow.  The  ordinary  constants 
of  the  hardened  peanut  oil  are  so  similar  to  those  for  lard  that  it  is  very  difficult  to 
distinguish  it  from  hog  fat,  but  the  phytosterol  of  the  3  vegetable  oils  investigated 
was  not  affected  by  the  treatment,  so  that  the  phytosterol  acetate  test  may  be 
relied  upon  for  the  detection  of  these  artificially  hardened  fats  when  they  are  used 
as  adulterants  for  lard,  margarine,  etc.  Cottonseed  oil,  after  treatment,  no  longer 
gives  the  Halphen  reaction,  but  sesame  oil  still  responds  to  the  Baudouin  test. 
Where  nickel  is  the  catalytic  agent  traces  of  it  will  be  found  in  the  finished  product 
if  there  were  any  appreciable  amount  of  free  acid  in  the  original  oil.  Bomer  con- 
cludes with  a  brief  report  of  preliminary  work  on  the  stereo-chemistry  of  the  glycer- 
ides  formed  and  the  requirements  which  the  new  product  will  have  to  meet  to  be 
acceptable  as  a  human  food. 

,  *  Bouant  (La  Galvanoplastie  (1894),  186)  makes  the  comment  that  after  having 
considered  nickel  as  dangerous  in  the  preparation  of  food,  it  is  now  recognized, 
on  the  contrary,  to  be  harmless.  Langbein  (Electro  Deposition  of  Metals  (1909), 
246)  observes  that  hot  fats  strongly  attack  nickel.  (Trans.  Am.  Electrochem. 
Soc.,  23,  116  (1913).) 

In  the  course  of  some  investigations  by  Gates  (J.  of  Phys.  Chem.  (1911),  15, 


EDIBLE  HYDROGENATED  OILS  147 

The  investigations  of  various  authorities,  such  as  Lehmann,  Thorns 
and  Miiller  have  shown  that  hardened  oils  used  for  edible  purposes  do 
not  cause  any  derangement  of  the  system  and  that  they  are  the  complete 
equivalent  of  animal  and  vegetable  fats  of  like  melting  point.*  Hydro- 
genated  fats  are  used  just  like  ordinary  fats  and  do  not  hinder  the 
assimilation  of  other  food  constituents.  The  nickel  content  on  a  daily 
consumption  of  100  grams  of  the  hardened  fat  is  stated  to  amount 
at  the  most  to  0.6  mg.  and  may  be  regarded  as  entirely  uninjurious. 
Hardened  fat  possesses  extremely  good  keeping  qualities,  and  this  is 
probably  also  the  case  with  margarine  prepared  from  it.f  Leimdorfer 
observes  that  hydrogenated  fats  change  in  odor  and  color  when  pre- 
served even  in  a  vacuum.  J 

A  careful  study  of  the  occurrence  of  nickel  in  edible  products  of 
various  kinds  has  been  made  by  Normann  and  Hugel.§  Hardened 
fats  prepared  with  the  aid  of  nickel  catalyzers,  and  intended  for  edible 
purposes,  contain  traces  of  nickel  which  they  state  amounts  to  two 
parts  per  million.  But  fats  which  have  been  treated  in  nickel-lined 
receptacles  show  fully  this  content  of  nickel.  Nickel-lined  ware  has 

97)  it  was  observed  that  many  of  the  common  metals  are  dissolved  appreciably  by 
oleic,  palmitic  and  stearic  acids,  with  evolution  of  hydrogen. 

The  Bureau  of  Animal  Industry  of  the  Department  of  Agriculture  is  investigat- 
ing the  matter  and  apparently  intends  to  determine  the  relative  degree  of  toxicity 
of  the  traces  of  nickel  in  the  form  existing  in  improperly  made  hydrogenated  oil. 
We  may  add  that,  so  far  as  can  be  ascertained,  the  Department  looks  kindly  upon 
the  advent  of  hydrogenated  oil  in  view  of  the  likelihood  that  it  is  destined  to  prove 
a  very  acceptable  substitute  for  higher-priced  animal  fats  and  does  not  propose, 
according  to  our  understanding,  to  venture  any  ruling  until  the  matter  has  had 
protracted  scrutiny. 

The  editor  of  the  National  Provisioner  comments  on  the  foregoing  as  follows: 

"It  is  evident  that  the  government  investigations  have  resulted  favorably,  since 
stearine  made  by  this  process  is  recognized  and  passed  by  the  Bureau  in  meat  inspec- 
tion, the  only  requirement  being  that  it  shall  be  stated  on  the  label  that  it  is  'Stearine 
made  from  cottonseed  oil'  to  indicate  that  it  is  manufactured  stearine  rather  than 
the  natural  article."  Editorial  note  in  National  Provisioner,  Dec.  27,  1913. 

Thompson  notes  that  some  criticism  has  been  directed  at  the  use  of  hardened 
oils  for  edible  purposes  on  the  ground  that  nickel  is  used  in  the  process,  but  the 
manufacturers  say  that  although  nickel  is  generally  used  none  of  it  is  left  in  the  oil, 
and  that  even  if  it  were  it  is  harmless,  as  shown  by  many  tests  with  animals  and 
with  human  "poison  squads. "  Consular  &  Trade  Reports,  Dept.  of  Commerce,  Jan. 
14,  1914,  171. 

*  See  also  "Gehartete  Pflanzenfette  in  der  Speisefettindustrie,"  Der  Seifen- 
fabrikant,  1914,  181. 

t  Halbmonatsschr.  f.  d.  Margarine-Ind.,  1914,  No.  4,  37;  Seifen.  Ztg.,  1914,  206. 

t  Seifen.  Ztg.,  1913,  1317;  J.S.C.I.,  1914,  206. 

§  Seifen.  Ztg.,  1913,  959. 


148  THE  HYDROGENATION  OF  OILS 

been  in  use  for  ten  years  or  more  and  during  this  period  many  people 
have  eaten  foodstuffs  containing  nickel,  without  any  injurious  effects 
being  noted.  Two  publications  have  already  discussed  the  matter 
to  some  extent,  one  being  by  Ludwig  *  and  the  other  by  Lehmann.f 
In  one  kilo  of  various  foodstuffs  these  investigators  found  the  follow- 
ing content  of  nickel: 

Ludwig  Lehmann 

Spinach 25-27  mgs.    Beef  and  bouillon 26-64  mgs. 

Peas 12-16     "      Potato   pulp    (equal  part 

Lentils  (acid) 35     "          of  water) 26-40 

Lentils  (boiled) 24     "      Spinach 22.4 

Sourkraut  54-129     "      Damson  plum  mixture ...  13.3 

Plums 35     "      Sourkraut 18-57 

Fruit  cooked  in  2  per  cent 

acetic  acid  solution ....     65-67 
Water,    salt    water,    flesh 

extract  and  milk 3.5-5.3 

The  whole  question  appeared  of  sufficient  importance  to  lead  Nor- 
mann  and  Hugel  to  repeat  this  work.  They  used  a  nickel  kettle  to 
prepare  the  food  material  and  ignited  the  product  in  a  silica  vessel 
to  obtain  the  content  of  ash.  Hydrochloric  acid  was  then  added  to 
the  ash  and  the  nickel  determined  by  Tschugaeff's  reagent. J  In  this 
manner  the  nickel  was  determined  gravimetrically  in  all  cases,  with 
the  exception  of  coffee.  In  this  latter  case  a  colorimetric  comparison 
with  a  nickel  solution  of  known  content  was  made. 

Thus  Normann  and  Hugel  found: 

Duration  of  Mgs.  of  nickel 

cooking,  in  one  kilo  of 

hours  material 

Coffee . i  0.03 

Apple |  46 

Cabbage f  83 

Red  cabbage 1  67 

Sourkraut 1J  127 

Kohlrabi 1  19 

Potato i  80 

One  of  these  investigators  used  a  kettle  of  this  character  for  a 
considerable  period  in  his  household.  The  food  for  the  use  of  the 
family  was  cooked  in  the  kettle  so  that  food  with  a  nickel  content, 
approximating  that  of  the  above  tabulation,  was  eaten,  but  no  ill 
effects  were  observed. 

*  Osterr.  Chem.  Ztg.,  Vienna,  Vol.  I,  No.  1,  1898. 
t  Arch,  fur  Hygiene,  Vol.  68  (1909),  421. 
j  Zeitsch.  f.  angew.  Chem.,  1907,  1844. 


EDIBLE  HYDROGENATED  OILS  149 

The  determination  of  nickel  in  fats  was  made  by  igniting  200  grams 
of  the  fat  in  a  silica  vessel,  dissolving  the  ash  in  hydrochloric  acid, 
saturating  the  solution  with  ammonia,  filtering  to  remove  any  pre- 
cipitate of  iron  or  alumina  and  evaporating  the  filtrate.  To  the 
residue  was  added  1  cc.  of  Tschugaeff's  reagent  (alcoholic  solution  of 
dimethylglyoxime)  and  ammonia  (when  a  rose  coloration  due  to  nickel 
occurs).  To  determine  the  nickel  quantitatively,  the  whole  residue 
was  dissolved  in  100  cc.  of  water  and  the  coloration  compared  with 
the  color  produced  by  adding  the  reagent  to  solutions  of  nickel  chloride 
of  known  content.  To  secure  a  constant  shade  it  was  found  desirable 
to  allow  the  solution  as  well  as  the  standard  to  stand  for  some  time, 
usually  over  night,  before  final  observations  were  made. 

Of  seven  samples  of  hardened  cottonseed  oil  examined,  four  samples 
contained  0.03  mg.  of  nickel  in  one  kilo.  One  sample  showed  a  rela- 
tively high  content,  0.075  mg.  of  nickel;  while  the  remaining  samples 
contained  0.02  mg.  of  nickel.  Palm  kernel  oil  showed  a  content  of 
nickel  ranging  from  0.017  to  0.1  mg.  of  nickel  per  kilo,  averaging 
around  0.02  mg.  Thus  it  will  be  noted  that  the  nickel  content  of 
these  fats  is  only  about  one-thousandth  part  of  that  found  in  foods 
prepared  in  nickel  kettles,  and  when  one  considers  that  fats  generally 
are  not  used  for  edible  purposes,  by  themselves,  but  simply  as  additions 
to  other  foods,  the  amount  of  nickel  furnished  by  hydrogenated  fatty 
material  amounts  to  so  very  little  that  the  consumption  of  such  food 
year  in  and  year  out  may  be  regarded  as  harmless. 

Even  in  fats  intended  for  technical  purposes,  the  amount  of  nickel 
is  small  as  compared  with  that  found  in  the  food  materials  above 
mentioned,  as  for  example: 

Nickel  in  one  kilo 

Hardened  fish  oil 3.3    mgs. 

Hardened  fish  oil 1.2    mgs. 

Hardened  fish  oil 3.2    mgs. 

Hardened  cottonseed  oil 0.85  mgs. 

Meyerheim*  notes  that  oils  which  are  to  be  hardened  for  edible  pur- 
poses should  be  washed  with  alkali  to  remove  fatty  acid  in  order  to 
reduce  the  tendency  to  solution  of  nickel  by  the  oil;  also  that  care 
should  be  taken  in  filter  pressing  to  completely  eliminate  the  particles 
of  nickel  catalyzer. 

The  propriety  of  using,  for  edible  purposes,  low-grade  fats  which 
have  been  deodorized  and  cleansed  by  hydrogenation  has  been  made 
the  subject  of  considerable  debate.  Bohm  states  f  that  when  Mege 

*  Fortschr.  Chem.  Phys.  and  Phys.  Chem.,  1913,  305. 
t  Seifen.  Ztg.  (1912),  1087. 


150  THE  HYDROGENATION  OF  OILS 

Mouries  was  working  on  the  production  of  artificial  butter  it  was  far 
from  his  mind  to  use  low-grade  fats  which  had  been  purified  by  chem- 
ical treatment  and  that  Boudet  prescribed  only  fat  of  the  best  quality 
obtained  from  cattle  slaughtered  on  the  same  day.  Later  when  Huet 
claimed  to  make  an  edible  product  by  thorough  treatment  of  bad 
tallow  with  aluminium  chloride  solution,  the  margarine  industry  was 
hit  a  severe  blow ;  for  after  such  a  proposal  the  opponents  of  artificial 
butter  sought  and  with  good  results  to  prejudice  the  public  against 
margarine. 

Although  to-day  in  a  margarine  establishment  there  is  to  be  found  the  uttermost 
cleanliness  as  regards  the  plant,  Bohm  states  that  this  is  not  true  of  the  raw  material 
before  it  comes  into  the  hands  of  the  margarine  manufacturer.  Even  though,  he 
declares,  development  of  oil  hardening  may  mean  a  great  advance  technically,  it 
is  coupled  with  such  an  opportunity  for  the  employment  of  low-grade  raw  materials 
that  it  is  likely  to  cause  anxiety  on  the  part  of  the  public.  In  particular  Bohm 
refers  to  the  utilization  of  hardened  fish  oil  in  the  margarine  industry  in  which 
application  technically  it  appears  entirely  suitable.  Hardened  fish  oil,  he  states, 
is  to  be  sure  a  chemically-changed,  completely  bacteria-free  product;  and  physio- 
logically is  uninjurious.  If,  however,  according  to  Bohm,  we  are  to  sanction  the 
chemical  treatment  of  fish  oil,  this  would  establish  an  important  precedent  for  the 
application  of  all  sorts  of  by-product  fats  and  cadaver  fats.  When  Hefter,  together 
with  other  experts,  formulated  for  the  margarine  industry  the  restriction  that  only 
those  fats  should  be  used  which  had  been  obtained  from  animals  slaughtered  under 
inspection,  every  consumer  as  well  as  every  manufacturer  of  margarine  was  affected. 
With  the  inauguration  of  margarine  manufacture  from  fish  oil  Bohm  further  states 
it  appears  not  improbable  that  conflict  with  the  present  laws  will  arise. 

Bohm  refers  to  the  assertion  of  Loock  regarding  renovated  butter  to  the  effect 
that  no  person  who  realizes  the  unpleasant  properties  of  the  original  material  would 
buy  such  butter,  a  statement,  says  Bohm,  which  can  certainly  apply  equally  well 
to  whale  oil  margarine.  Loock  also  cites  a  decision  to  the  effect  that  no  doubt 
exists  that  a  food  product  is  to  be  looked  upon  as  unfitted  for  consumption  when 
the  raw  material  possesses  a  loathsome  nature,  irrespective  as  to  whether  the  material 
through  chemical  treatment  has  been  freed  from  such  undesirable  properties. 

As  to  the  loathsome  nature  of  whale  oil,  Bohm  asserts  that  one  need  only  note 
the  character  of  the  methods  employed  in  obtaining  it  in  order  to  appreciate  its 
undesirable  nature.  He  maintains  that  a  great  part  of  the  carcasses  of  whales  are 
allowed  to  stand  days  at  a  time  before  they  are  worked  up.  Bohm  indignantly 
declares  the  proposal  to  make  an  edible  fat  out  of  half-rotten  whales  which  are 
treated  in  the  hovels  of  the  natives  must  naturally  excite  disgust.  Perhaps,  he 
says,  a  manufacturer  of  artificial  butter  may  be  able  to  use  hardened  fish  oils  in 
spite  of  the  pure  food  laws,  but  may  yet  come  into  contact  with  the  criminal  courts, 
for  when  one  buys  margarine  he  expects  to  obtain  freshly  prepared  beef  fat  and  not 
a  chemically-changed  fish  oil. 

While  this  contention  of  Bohm  may  not  be  sound  in  some  respects 
it  is  noted  here  for  the  sake  of  completeness.  Naturally  such  an 
attack  against  a  new  and  promising  use  for  whale  oil  has  not  passed 


EDIBLE  HYDROGENATED  OILS  151 

unnoticed.  See  rejoinder  by  Lieber  in  Seifensieder  Zeitung  (1912), 
1188,  and  editorial  comment  adverse  to  Bohm,  also  the  opinion  of 
Keutgen.* 

An  oil  which  has  been  used  so  extensively  by  physicians  all  over 
the  world  as  a  remedial  food  for  children  Lieber  believes  cannot  be 
looked  upon  as  unsafe  for  human  consumption.  He  calls  attention 
to  the  hardy  nature  of  the  Eskimo  whose  principal  or  sole  food  is  the 
blubber  of  the  whale  and  seal.  Furthermore,  he  contends  that  if 
the  carcasses  of  whales  were  allowed  to  decompose,  the  oil  which 
resulted  would  be  of  low  grade  and  the  pecuniary  loss  would  be  con- 
siderable. By  the  present  system  as  soon  as  a  whale  is  harpooned 
it  is  hoisted  aboard  the  whaling  ship  and  immediately  rendered,  the 
several  grades  of  oil  obtained  being  pumped  to  separate  tanks.  Every 
effort  is  made  to  produce  the  maximum  yield  of  No.  0  and  No.  1  oil 
because  of  the  relatively  high  prices  these  bring. 

Until  seven  years  ago  there  was  only  a  limited  demand  for  whale 
oil,  which  was  mainly  used  for  the  production  of  glycerine  and  fatty 
acids.  It  is  now  hydrogenated,  for  soap-making  purposes,  but  in 
Offerdahl's  opinion  hardened  whale  oil  is  suitable  for  food.  With 
regard  to  the  traces  of  nickel  present  in  the  hardened  oil,  experiments 
showed  that  when  small  amounts  of  nickel  powder  were  taken  daily 
no  ill  effects  were  experienced,  and  that  99.8  per  cent  of  the  metal 
was  rapidly  excreted  from  the  system.  Hardened  whale  oils  were 
found  to  be  free  from  bacteria,  f 

The  Halbmonatschrift  f.  d.  Margarineindustrie  (Dusseldorf)  discusses  the  ques- 
tion of  the  prohibition  of  the  use  of  whale  oil  in  the  edible  fat  industry  (Seifen.  Ztg. 
(1914),  30)  and  from  this  discussion  the  following  is  noted, J  —  Ever  since  the  dis- 
covery was  made  of  preparing  an  odorless  and  tasteless  fat  from  whale  oil  by  the 
hardening  process  it  has  been  taken  for  granted  in  those  circles  which  are  antago- 
nistic to  the  further  development  of  the  margarine  and  artificial  edible  fat  industry 
that  hardened  fish,  seal  or  whale  oil  could  be  used  in  the  preparation  of  butter  sub- 
stitutes. This  suspicion  was  all  the  greater  because  of  the  increase  in  the  last  few 
years  in  the  cost  of  most  of  the  raw  materials  used  in  the  margarine  industry.  It 
has  been  customary  for  the  agricultural  opponents  of  butter  substitutes  to  condemn 
the  raw  products  from  which  these  products  are  obtained  and  in  this  way  to  seek 
to  make  this  indispensable  article  of  food  repulsive  to  the  consumer.  But  in  recent 
years  the  knowledge  that  margarine  practically  does  not  influence  the  price  of 
natural  butter,  and  therefore  does  not  enter  into  competition  with  it,  has  gained 
some  little  headway.  Dr.  Vieth,  Director  of  the  Dairy  Station  in  Hameln  (an 
authority  in  his  line)  has  acknowledged  this  to  be  a  fact.  If  the  margarine  does  not 

*  Seifen.  Ztg.  (1914),  89. 
t  Offerdahl,  Ber.  (1913),  558. 

t  See  also  the  views  of  the  Deutsche  Margarine  Zeitschrift  (Seifen.  Ztg.  (1914), 
118). 


152  THE  HYDROGENATION  OF  OILS 

harm  the  butter  industry,  the  bottom  is  taken  out  of  the  agitation  which  has  been 
going  on  for  over  a  decade  against  the  manufacture  of  substitutes.  In  spite  of 
this  (Molkerei  Zeitung,  1913)  space  has  been  lent  anew  to  the  suspicion  that  the 
raw  materials  used  in  the  production  of  margarine  cannot  be  entirely  without  effect. 

Edible  fats,  such  as  hardened  palm-kernel  oil,  cottonseed  oil,  etc.,  which  have 
recently  been  introduced  into  the  manufacture  of  margarine  are  thoroughly  tested 
by  government  officials  and  scientific  experts.  The  suspicion  that  infectious  raw 
materials  might  be  utilized  can  therefore  apply  only  to  the  possible  use  of  hardened 
whale  and  seal  oil.  In  order,  however,  to  prevent  the  spread  of  this  idea  and  in 
order  thereby  to  prevent  a  new  danger  to  the  butter  substitute  industry,  the  Duessel- 
dorfer  Margarine  Zeitschrift  suggests  a  legal  prohibition  of  the  use  of  whale  oil  in 
the  edible  fat  industry. 

It  is  supposed  that  the  official  foodstuff  investigators  will  eventually  aid  this 
proposal.  Its  necessity  is  shown  by  the  fact  that  an  effort  has  been  made  from 
foreign  countries  to  induce  German  margarine  factories  to  use  whale  oil.  The 
suggestion  that  well-known  and  reputable  margarine  factories  have  already  started 
to  use  whale  oil  has  been  shown  to  be  without  foundation  and  is  thought  to  be 
out  of  the  question  for  the  future.  In  order  that  no  margarine  made  from  whale 
oil  may  reach  the  German  consumer  because  of  unscrupulous  manufacturers  (and 
in  that  way  the  good  name  of  a  product  which  has  been  established  only  after  many 
years  of  effort  be  brought  into  ill  repute)  but  one  remedy  can  be  suggested:  the 
prohibition  of  whale  oil  for  food  purposes.  The  trade  journal  of  the  margarine 
industry  points  out  that  such  a  value  is  placed  by  all  classes  of  society  upon  mar- 
garine that  the  thought  of  utilizing  any  raw  material  repulsive  to  individual  consumers 
ought  to  meet  with  vigorous  opposition.  It  is  evident  from  the  editorial  comment 
at  the  close  of  this  article  that  the  Seifensieder  Zeitung  is  not  in  accord  with  the 
drastic  views  expressed  in  the  foregoing.* 

On  the  subject  of  hydrogenated  edible  oils  but  little  has  appeared 
in  the  literature. f  A  number  of  patents  discuss  various  products  and 
methods  of  preparation. 

An  edible  oil  composition  is  described  by  Ellis  J  comprising  hydro- 
genated cottonseed  oil  and  cocoanut  oil,  the  mixture  being  beaten 
with  air  to  improve  the  color  of  the  product.  The  following  formula 
and  method  of  treatment  are  given:  Ninety  parts  cottonseed  oil  are 
mixed  with  ten  parts  of  cocoanut  oil  and  the  mixture  subjected  to  the 
action  of  hydrogen  at  a  temperature  of  from  150°  to  160°  C.,  in  the 
presence  of  finely-divided  nickel  so  as  to  convert  a  large  proportion 
of  the  unsaturated  into  saturated  material.  A  solid  composition  is 
produced  which  is  then  subjected  to  aeration  which  may  be  carried 
out  by  beating  the  hydrogenated  product  with  rapidly  revolving 

*  Further  comment  by  Keutgen  on  the  same  subject  appears  in  Seifen.  Ztg. 
(1914),  171. 

t  In  an  article  on  "Hydrogenated  or  Hardened  Fat,"  appearing  in  the  National 
Provisioner,  Sept.  27,  1913,  104,  Hall  observes  that  hydrogenation  is  one  of  the 
greatest  advances  ever  made  in  the  fat  and  oil  field. 

t  U.  S.  Patent  1,037,881,  Sept.  10,  1912. 


EDIBLE  HYDROGENATED  OILS  153 

paddles  until  a  sufficient  quantity  of  air  is  incorporated  in  the  product, 
in  a  finely-vesiculated  condition  to  produce  a  material  of  the  proper 
consistency  and  light  colored  appearance.  Another  statement  *  gives 
details  of  a  hydrogenated  butter  substitute  in  which  various  hydro- 
genated  and  normal  oils  are  incorporated  to  make  a  fat  approximating 
the  melting  point  of  butter,  with  which  is  mixed  milk,  etc.,  to  produce 
a  variety  of  margarine.  These  compositions  should  ordinarily  have 
a  melting  point  considerably  less  than  the  temperature  of  the  human 
body,  so  that  when  the  material  is  taken  into  the  mouth,  it  immedi- 
ately melts  and  does  not  leave  a  greasy  sensation  on  the  tongue  and 
walls  of  the  mouth.  It  is  generally  desirable  to  carry  the  hydrogena- 
tion  treatment  to  a  point  where  a  product  of  rather  firm  consistency 
is  secured.  This  produces  a  material,  however,  which  is  of  too  high 
a  melting  point  for  the  production  of  a  vegetable  butter  composition. 
Hence  it  is  then  pressed  to  remove  the  excessive  amount  of  stearin. 
In  the  case  of  cottonseed  oil,  it  is  stated  that  it  is  desirable  to  hydro- 
genate  until  the  iodine  number  falls  to  about  80.  The  oil  may  then 
be  cooled  to  about  30°  C.,  and  allowed  to  stand  for  a  time  and  pressed. 
Afterwards  it  is  warmed  to  render  it  entirely  fluid,  and  is  incorporated 
with  milk  material.  Suitable  material  of  this  character  is  ordinary 
full  milk  or  skim  milk  or  butter-milk,  sterilized  milk,  sour  milk  or 
milk  which  has  been  specially  fermented.  Coloring  material,  such 
as  ordinary  butter  color,  may  be  added.  Also  a  flavoring  compound, 
such  as  cumarin  and  various  esters  and  aldehydes,  such  as  those  of 
valerian  and  capryl  bodies,  may  be  added.  In  order  to  give  the  prod- 
uct the  property  of  browning,  when  heated  in  a  skillet,  bodies  such 
as  egg  yolk,  milk  sugar,  lecithin  or  finely-powdered  casein  may  be 
introduced. 

A  suitable  oil  base  having  been  derived  in  this  manner,  the  oily 
material  is  emulsified  with  the  milk  material  to  thoroughly  mix  the 
latter  with  the  fatty  body.  For  100  parts  of  fatty  material  about 
30  to  60  parts  of  full  milk  or  perhaps  50  to  80  parts  of  skim  milk  are 
suitable  proportions.  In  the  summer  months  a  stiffer  composition  is 
required  than  in  the  winter  months  and  the  fatty  material  should  be 
compounded  to  give  a  material  melting  at  the  proper  point  with 
reference  to  seasonal  temperatures.  In  emulsifying  it  is  desirable 
to  put  a  portion  of  the  milk  in  the  beating  apparatus,  and  to  stir  for 
a  short  time.  In  the  case  of  full  milk,  beating  for  10  minutes  or  so 
causes  a  separation  of  the  butter  fat.  The  oil  may  then  be  added  in 
portions,  beating  thoroughly  until  the  composition  is  well  incorpo- 
rated. The  remainder  of  the  milk  and  fatty  material  may  be  added 
*  Ellis,  U.  S.  Patent  1,038,545,  Sept.  17,  1912. 


154  THE  HYDROGENATION  OF  OILS 

from  time  to  time,  and  the  temperature  of  the  mixture  should  prefer- 
ably be  maintained  between  30°  and  40°  C.  When  the  composition 
has  become  thoroughly  incorporated,  it  is  run  from  the  apparatus  into 
a  cooling  device  which  cools  the  emulsified  composition  rapidly.  It  is 
then  ready  to  be  rolled  and  kneaded  to  remove  the  excess  of  water, 
etc.,  after  which  treatment  the  material  is  formed  into  the  desired 
shape  for  shipment.  The  coloring  material  and  salt  and  also  flavoring 
material  may  be  added  during  the  emulsification  process  if  desired. 

The  use  of  hardened  oil  in  preparing  oleomargarine  compositions 
is  the  basis  of  French  Patent  458,611,  of  1913,  to  Deveaux. 

Hydrogenated  soya  bean  oil  *  has  been  recommended,  as  well  as 
hydrogenated  vegetable  oil  and  animal  fats  mixed  to  form  lard-like 
products  of  varying  composition.  When  employing  cocoanut  oil  in 
such  compositions  it  is  desirable  to  hydrogenate  it.  To  be  sure,  cocoa- 
nut  oil  usually  has  an  iodine  value  of  only  7  to  10,  which  is  indicative 
of  the  small  proportion  of  unsaturated  bodies  present.  But,  in  spite  of 
this,  in  order  to  secure  a  permanent  product,  which  does  not  separate 
or  grow  lumpy  on  standing,  and  which  remains  in  a  perfectly  neutral 
condition  for  a  long  period  of  time,  even  when  exposed  to  the  air,  it 
is  desirable  that  the  iodine  number  of  the  cocoanut  oil  should  be 
reduced  to  practically  zero,  if  larger  proportions  than  30  per  cent  or 
thereabout  are  incorporated  with  hydrogenated  soya  bean  or  cotton- 
seed oil. 

An  edible  product  of  a  superhydrogenated  character  f  is  obtained 
by  carrying  the  degree  of  hydrogenation  beyond  the  actual  titer  re- 
quired and  then  pressing  to  remove  some  of  the  harder  material  so 
that  the  final  titer  of  the  expressed  fat  is  that  of  lard,  butter  or  what- 
ever other  titer  may  be  required.  Most  oils  of  a  vegetable  nature 
and  some  animal  oils  contain  from  traces  up  to  considerable  quantities 
of  highly-unsaturated  bodies,  including  those  of  the  linoleic  and  lino- 
lenic  group.  These  and  other  similar  bodies  are  very  sensitive  to 
oxidation  and  lend  instability  to  edible  oil  products  of  this  character 
by  their  tendency  to  change  chemically  and  thus  alter  the  flavor  of 
the  material.  These  bodies  may  be  saturated  by  very  careful  hydro- 
genation up  to  the  degree  of  consistency  required  in  the  edible  prod- 
uct, but  such  hydrogenation  is  difficult  to  carry  out  commercially  on 
a  large  scale  with  the  assurance  that  the  product  will  run  uniform  in 
quality.  By  saturating  these  bodies  with  hydrogen  to  an  excessive 
degree  as  regards  final  consistency,  these  bodies  lose  their  identity 
and  become  substantially  free  of  odor  of  origin  and  tendency  to  rancid- 

*  Ellis,  U.  S.  Patent  1,047,013,  Dec.  10,  1912. 
t  Ellis,  U.  S.  Patent  1,058,738,  April  15,  1913. 


EDIBLE  HYDROGENATED  OILS  155 

ify  or  otherwise  be  decomposed.  By  hydrogenating  cottonseed  or 
corn  oil  or  similar  oils  to  materially  reduce  the  iodine  number,  the 
more  sensitive  double  bonds  are  saturated  with  hydrogen  and  thereby 
eliminated  and  oxidation  tendency  is  reduced  to  a  minimum.  Ap- 
parently the  complete  elimination  of  all  the  double  bonds  character- 
istic of  the  linoleic  type  is  more  difficult  than  the  removal  of  the  double 
bonds  characteristic  of  the  linolenic  type,  so  that  control  over  this 
seeming  selective  action  during  hydrogenation  when  saturating  up 
to  a  given  degree  of  consistency  from  a  given  oil  is  difficult,  if  not 
impossible,  under  ordinary  conditions  of  hydrogenating.  If,  however, 
the  oil  is  overhydrogenated  so  that  a  more  consistent  fat  is  acquired 
than  is  actually  desired  for  an  edible  product,  the  unstable  bodies 
thus  may  be  completely  transformed.  In  order  to  secure  the  degree 
of  consistency  desired  the  hot  hydrogenated  fat  is  gradually  cooled 
to  about  30°  C.,  when  the  temperature  may  be  maintained  between 
25°  to  35°  C.,  or  so  for  several  hours  to  induce  crystallization  or  ball- 
ing of  the  high  melting  point  compounds.  The  mass  is  then  pressed 
to  the  desired  degree.  Such  a  superhydrogenated  pressed  product 
which  may  be  made  either  of  butter-like  or  of  lard-like  consistency 
is  stable  in  storage  and  is  not  liable  to  coagulate  on  standing  with 
the  formation  of  objectionable  masses  of  granulous  stearin-like 
bodies. 

It  has  been  noted  when  a  vegetable  oil  such  as  cottonseed  oil  is 
hydrogenated  directly  until  of  the  consistency  desired  that  on  cool- 
ing frequently  it  tends  to  granulate  unless  chilled  or  very  rapidly 
cooled.  This  is  objectionable  in  culinary  operations  as  an  initial 
lard-like  body  after  once  heating  and  slow  cooling  in  the  air  often 
forms  relatively  hard  granules  of  stearin-like  bodies  which  look  like 
little  balls  of  coagulated  material  and  separating  as  they  do  from  the 
fluid  oil  under  some  circumstances  give  the  product  the  appearance  of 
having  curdled  or  decomposed.  By  super-hydrogenating  and  press- 
ing to  the  point  required  the  granulating  stearins  or  stearin-like  bodies 
are  eliminated  to  a  greater  or  less  extent  and  less  easily  crystal- 
lizing or  non-granulating  stiffening  bodies  remain  tending  from  their 
amorphous  texture  to  better  maintain  the  original  consistency  and 
appearance  of  the  product  in  repeated  culinary  use. 

The  Boyce  process*  of  producing  an  edible  compound  consists  in 
preparing  a  mixture  of  synthetic  stearin  by  the  action  of  hydrogen 
in  the  presence  of  a  catalyzer  upon  a  previously  unsaturated  oil  or 
fat,  the  latter  being  subjected  to  the  catalytic  action  of  hydrogen  to  a 

*  Boyce,  U.  S.  Patent  1,061,254,  May,  6, 1913,  assigned  to  the  American  Cotton 
Oil  Co. 


156  THE  HYDROGENATION  OF  OILS 

degree  sufficient  to  convert  the  required  fraction  of  the  oil  into  syn- 
thetic stearin.  The  hydrogenation  process  is  arrested  at  the  point 
when  the  stearin  is  found  to  be  present  in  the  amount  of  about 
20  per  cent  of  the  entire  body  of  the  oil.  Boyce  states  that  by  arrest- 
ing the  action  at  this  point  there  will  remain  a  mixture  of  the  unsatu- 
rated  oil  and  the  synthetic  stearin  produced  by  the  hydrogenation 
of  a  portion  of  the  oil. 

A  hydrogenated  fatty  food  product  containing  hydrogenated  corn 
oil  has  been  described.*  When  corn  oil  is  suitably  hydrogenated,  a 
product  is  derived  which  has  the  property  of  improving  the  stability 
of  hydrogenated  cottonseed  oil  or  similar  hydrogenated  oils  which 
tend  to  granulate.  Also  it  is  stated  that  hydrogenated  cocoanut  oil 
may  be  used  as  a  fluxing  agent  for  chocolate  in  the  manufacture  of 
confectionery.  The  melting  point  of  the  fatty  flux  should  preferably 
be  about  90°  to  100°  F.  Hydrogenated  cocoanut  oil  olein  may  be 
used  in  a  similar  manner.  The  manufacture  of  the  coating  of  choco- 
late creams  calls  for  a  relatively  high  melting  point  fat  which  incor- 
porates readily  with  chocolate  and  does  not  impair  its  flavor.  Cocoa 
butter  is  especially  desired  on  this  account,  but  is  relatively  expensive. 
Cocoanut  oil  melts  so  easily  that  in  hot  weather  candies  made  with  it 
soften  very  quickly  when  handled.  Cocoanut  oil  also  has  a  tendency 
to  rancidify.  By  hydrogenation  of  an  oil  assimilable  with  chocolate 
the  exact  melting  point  desired  may  be  obtained  and  a  stable  compo- 
sition secured. 

Hydrogenated  oil  of  high  titer,  as  stated,  may  be  mixed  with  un- 
hydrogenated  oil  to  form  a  body  of  a  consistency  suitable  for  use  as 
a  substitute  for  lard.  For  example,  hydrogenated  cotton  oil  of  a  titer 
of  say  52°  C.  (fatty  acids)  may  be  melted  and  incorporated  with  four 
times  its  weight  or  so  of  ordinary  refined  or  deodorized  cottonseed 
oil  so  as  to  form  on  cooling  a  white,  opaque  fatty  material  of  the  con- 
sistency of  ordinary  lard.  The  product  made  in  this  manner  is  not 
always  sufficiently  stable.  Not  infrequently  in  a  short  time  it  will 
lose  its  opacity  to  a  considerable  degree  and  will  take  on  an  appear- 
ance more  suggestive  of  petrolatum  than  lard.  Sometimes  this  change, 
which  may  be  due  to  a  tendency  to  form  solid  solutions  of  certain 
types,  occurs  irregularly  in  layers  or  isolated  zones  which  give  the 
product  a  curious  mottled  appearance,  and  this  striated  effect  taking, 
place  in  the  containers  during  storage  so  changes  the  product,  physically 
at  least,  that  it  is  regarded  as  damaged  or  unfit  for  use  by  those  accus- 
tomed to  the  normal  appearance  of  lard.  By  disseminating  through 
a  fatty  basis  of  a  melting  point  and  consistency  approaching  that  of 
*  Ellis,  TJ.  S.  Patent  1,067,978,  July  22,  1913. 


EDIBLE  HYDROGENATED  OILS  157 

lard,  a  quantity  of  fatty  material  of  higher  titer  so  as  to  form  floccula- 
tions  of  a  high  titer  product  uniformly  disseminated  through  the 
fatty  basis,  a  product  of  better  "  color  stability  "  is  secured.*  The 
material  of  the  relatively  higher  titer  may  be  denominated  the  stabilizer 
and  the  proportions  of  fatty  basis  and  stabilizer  as  well  as  their  melt- 
ing points  and  titers  may  be  varied  to  meet  various  conditions  of  a 
climatic  nature. 

As  an  illustration  one  may  take  to  make  the  fatty  basis,  6  parts  of  hydrogenated 
cottonseed  oil  of  a  titer  ranging  between  52°  to  54°  C.  (fatty  acids)  and  34  parts  of 
refined  and  deodorized  cottonseed  oil.  A  thorough  mixture  is  secured  by  the  aid 
of  heat  and  when  well  incorporated  the  melted  product  is  chilled  rapidly  in  a  thin 
layer  by  feeding  onto  a  chilled  roll  which  is  kept  in  constant  rotation  and  from  which 
the  solidified  product  is  removed  in  layers  by  a  scraper.  This  product  when  prop- 
erly set  has  a  consistency  approaching  that  of  ordinary  lard.  The  stabilizer  is  pre- 
pared by  incorporating  3  parts  of  hydrogenated  cottonseed  oil  of  the  same  titer  as 
that  used  in  making  the  fatty  basis,  with  5  parts  of  refined  and  deodorized  cottonseed 
oil.  By  heating  the  hardened  oil  with  the  deodorized  oil  the  requisite  mixture  is 
obtained.  As  in  making  the  fatty  basis,  the  stabilizer  is  likewise  chilled  to  form  a 
solid,  preferably  in  thin  layers,  and  the  two  products  are  mixed  in  powerful  mixing 
apparatus  until  the  stabilizer  is  well  disseminated  through  the  fatty  basis.  To 
secure  a  desirable  distribution  both  the  fatty  basis  and  the  stabilizer  may  be  fed 
onto  the  same  chill  roll  in  a  series  of  adjacent  or  alternate  streams,  or  the  fatty 
basis  may  be  allowed  to  fall  on  the  chill  roll,  and  when  it  has  progressed  a  distance 
sufficient  to  solidify  but  not  to  stiffen  it  fully,  the  stabilizer  is  applied  as  a  super- 
posed coating  adherent  to  and  slightly  intermingled  at  the  contacting  surfaces, 
with  the  fatty  basis.  This  composite  film  is  removed  by  the  scraper  and  is  then 
"pugged"  or  beaten.  As  the  melting  point  of  the  stabilizer  is  preferably  consider- 
ably higher  than  that  of  the  fatty  basis,  the  former  congeals  more  quickly,  so  that 
although  the  superposed  film  is  somewhat  insulated  from  the  chill  roll  by  the  fatty 
basis  film  yet  the  solidification  of  the  upper  layer  is  usually  rapid  enough  to  prevent 
material  solution  or  interfusion  of  the  two  heterogeneous  layers. 

Further  modifications  are  the  following:  Eighty  parts  of  cottonseed  oil  are  mixed 
with  fifteen  parts  of  hydrogenated  oil  of  a  titer  of  48  (fatty  acids).  This  is  chilled 
and  mixed  with  five  parts  of  melted  42°  C.  titer  hydrogenated  or  hard  oil,  or  fat. 
Likewise  one  can  superpose  on  a  basis  of  34  to  38  titer  about  20  per  cent  of  40  to 
42  titer.  Cottonseed  oil  may  be  hydrogenated  to  37  titer,  chilled  as  described  and 
similarly  incorporated  with  about  10  to  20  per  cent  cottonseed  oil  hydrogenated 
to  40  to  42  titer.  Thus  there  may  be  obtained  a  lard-like  or  otherwise  consistent 
fatty  material  having  its  main  titer  to  a  considerable  degree  influenced  so  that  the 
product  may  have  the  desired  soft  consistency  of  ordinary  lard  while  actually  con- 
taining bodies  which  if  melted  into  the  fatty  basis  would  raise  the  melting  point 
and  consistency. 

Palm  oil,  suitably  hydrogenated,  has  been  recommended  for  use 
in  edible  fat  products,  t 

*  Ellis,  U.  S.  Patent  1,070,331,  Aug.  12,  1913. 
t  Ellis,  U.  S.  Patent  1,087,161,  Feb.  17,  1914. 

The  fatty  acids  of  Kaya  oil  have  been  hydrogenated  by  Ueno  (Chem.  Rev.  u. 
d.  Fett.  u.  Harz.  Ind.  (1913),  209)  who  thereby  obtained  fatty  acida  melting  at 


158  THE  HYDROGENATION  OF  OILS 

Wilbuschewitsch  *  regards  his  process  as  applicable  to  the  treat- 
ment of  all  unsaturated  acids  and  their  glycerides,  as  well  as  for 
waxes  and  other  alcoholic  fatty  substances.  From  castor  oil  there  is 
obtained  a  product  which  melts  at  83°  C.  The  finished  fat  can  be 
hydrolyzed  and  the  fatty  acids  distilled.  For  example,  from  cotton- 
seed oil  there  may  be  obtained  fatty  acids  which  melt  up  to  71°  C. 
and  make  excellent  candles.  After  suitable  refining  the  products 
may  yield  satisfactory  alimentary  fats  if  the  reduction  is  only  carried 
so  far  that  the  melting  point  is  between  28°  and  34°  C.  Thus  he 
finds  from  castor  oil  there  may  be  made  a  product  which  is  odorless 
and  tasteless  but  retains  the  other  properties  of  castor  oil.  So  also 
from  cod  liver  oil  and  other  fish  oils  there  may  be  made  butter  substi- 
tutes, or  from  vegetable  oils  substitutes  for  cocoa  butter.  Oils  treated 
by  the  process  lose  their  specific  odor.f 

65.5°  C.  The  hydrogenation  of  the  material  was  carried  out  in  alcohol  solution  using 
platinum  black  as  a  catalyzer.  Kaya  oil  as  employed  for  edible  purposes  is  liquid 
and  yellow  in  color. 

*  U.  S.  Patent  1,024,758,  April  30,  1912. 

f  The  keeping  properties  of  some  hardened  oils  examined  by  Knapp  (Analyst, 
1913,  102)  were  found  to  be  remarkably  good.  Although  prepared  nearly  a  year 
and  a  half  previously,  and  having  often  been  exposed  to  damp  air,  yet  these  samples 
showed  no  signs  of  rancidity.  The  acidity  (0.7  per  cent  as  oleic  acid)  did  not  appre- 
ciably change  during  the  period  of  observation. 


CHAPTER  X 

USES   OF  HYDROGENATED   OILS   AND   THEIR  UTILIZA- 
TION IN   SOAP  MAKING 

USES  OF  HYDROGENATED  OILS 

Liquid  fats  and  fatty  acids  are  essentially  cheaper  than  solid  fats 
and  fatty  acids,  and  the  ability  to  prepare  from  ordinary  liquid  fatty 
oils  a  fatty  body  of  almost  any  desired  degree  of  consistency  or  hard- 
ness renders  hydrogenation  especially  attractive  in  the  production 
of  edible  fats  and  soap-making  materials.  These  are,  undoubtedly, 
two  of  the  most  important  applications,  although  hydrogenated  oils 
are  likely  to  have  a  rather  wide  use  in  the  arts.  In  the  manufacture 
of  insulating  compositions  and  lubricants,  for  example,  the  hydro- 
genated fats  may  be  used  to  advantage.  In  the  tanning  industry 
the  stearin  produced  by  hydrogenation  is  being  used  as  a  substitute 
for  oleo-stearin. 

The  physical  and  chemical  properties  *  of  hardened  oils,  particularly 
the  hardened  fish  oils,  indicate  that  these  products  are  useful  in  the 
manufacture  of  lubricants  and  that  they  may  be  used  as  a  substitute 
for  tallow  in  the  preparation  of  various  lubricating  compounds.!  In 
compounding  preparations  of  this  character,  the  requisite  amount  of 
hardened  oil  is  added  to  the  oil  base  employed,  the  mixture  being 
heated  to  secure  satisfactory  incorporation,  and  then  is  cooled,  when 
it  is  ready  for  use.  The  better  grades  of  hardened  fish  oil  also  can 
be  used  alone  as  a  substitute  for  acid-free  machine  tallow. 

A  review  of  the  soap  trade  of  the  United  Kingdom  for  1913  is  significant  in 
indicating  decreased  requirements  of  several  of  the  staple  raw  materials,  which  con- 
dition, rather  than  suggestive  of  any  decline  in  the  production  of  soap,  marks  a 
greater  dependence  upon  supplies  which  have  been  brought  within  practical  oper- 
ation largely  through  the  hydrogenating  process  for  hardening  oils.  To  quote 
from  the  report  on  this  subject: 

"It  is  of  the  greatest  tnoment  that  the  European  soap  maker  has  found  in  the 
hardened  oils  produced  by  the  hydrogen  process  very  considerable  relief  from  factors 
that  must  have  driven  values  very  much  higher,  had  not  this  new  source  of  supply 
come  into  actual  operation. " 

*  Seifen.  Ztg.  (1912),  1092. 

t  Hydrogenated  fats,  Leimdorfer  states  (Seifen.  Ztg.  (1913),  1317),  can  be  used 
in  the  preparation  of  lubricants  and  in  tanning  operations. 

159 


160  THE  HYDROGENATION  OF  OILS 

"  English  manufacturers  as  a  rule  are  quick  to  turn  to  advantage  any  opportunity 
to  exploit  new  methods  and  processes  in  their  industries,  and  the  recognition  of  the 
practical  application  of  hydrogenated  oils  in  such  an  important  field  as  soap  making 
is  a  development  of  much  interest  to  the  affected  trades  in  this  country,  where  the 
process  in  its  general  relationship  to  the  soap  and  lard  compound  industries  is  in  a 
more  or  less  experimental  stage.  According  to  the  English  soap  trade  report  the 
losses  in  three  of  the  leading  materials  available  for  home  consumption,  as  measured 
by  the  excess  of  imports  over  exports  in  1913,  were  3532  tons  of  tallow,  1656  tons  of 
palm  oil  and  2240  tons  of  cocoanut  oil.  Exports  of  soap  from  the  United  Kingdom 
last  year  were  heavier  (1732  tons),  while  imports  from  foreign  countries  were  lighter 
by  2194  tons.  As  a  result  of  the  strides  in  the  hardening  of  materials  for  soap  pro- 
duction by  hydrogenation,  whale  and  linseed  oils  are  now  accorded  an  established 
place  in  the  Kingdom's  soap  industry.  The  total  capacity  of  the  hardening  plants 
in  Europe,  including  the  United  Kingdom,  is  given  as  220,000  tons  of  oil,  although 
some  of  the  views  expressed  in  the  local  trade  place  it  to  300,000  tons.  A  good  part 
of  the  American  Unseed  oil  export  trade  last  year  has  been  attributed  to  the  heavier 
requirements  for  the  soap  kettle  through  the  hydrogenation  process,  and  crushers 
and  dealers  have  been  buoyed  to  keener  expectations  for  this  year's  foreign  business. 
Conditions  in  other  fields  in  which  linseed  oil  enters  must,  however,  be  reckoned 
upon  as  contributing  factors.  Persistent  attempts  have  been  made  to  induce  our 
soap  makers  to  adapt  hardened  linseed  oil  to  their  service,  and  while  sales  of  round 
parcels  have  been  made  for  this  account,  so  far  as  is  known  none  of  the  purchasers 
has  been  encouraged  to  put  the  oil  into  actual  test.  The  favorable  market  condi- 
tions for  competing  fats  in  the  soap  field  may  have  accounted  for  the  attitude  of 
makers  toward  linseed  oil  for  this  particular  purpose." 

"Probably  the  greatest  headway  in  the  application  of  the  hydrogenating  hardening 
process  in  this  country  has  been  in  the  field  of  edible  products  in  which  cottonseed 
oil  has  entered  on  the  most  liberal  scale.  It  was  through  this  means  that  the  domes- 
tic consumption  of  refined  oil  during  the  last  crop  year  so  surpassed  the  general 
expectations  of  the  trade  that  the  principal  markets  abroad  were  scoured  last  sum- 
mer to  reclaim  any  supplies  of  our  oil  that  might  be  available,  and  foreign  producing 
sources  were  also  called  upon  to  help  relieve  the  stringency  here."  * 

Auerbachf  considers  the  hydrogenation  process  responsible  for  an  advance  in  the 
price  of  fish  oils  so  that  they  will  be  of  doubtful  benefit  to  the  soap  industry.  Also 
he  states  that  the  so-called  burned  odor  which  was  noticeable  in  soap  made  from 
hardened  fats  is  said  to  have  been  overcome.  Besides  fish  and  whale  oil,  he  notes 
that  castor  oil  is  treated  to  some  extent.  The  hardened  castor  oil  is  used  for  insula- 
tion purposes  in  the  electrical  field. 

HYDROGENATED  OILS  IN  THE  SOAP  INDUSTRY 

The  developments  in  oil  hydrogenation  have  brought  to  the  soap 
industry  an  innovation  of  fundamental  importance  in  the  domain  of 
raw  materials.  The  soap  manufacturer,  no  longer  well  able  to  pur- 
chase the  best  grade  of  fats  in  face  of  the  high  prices  paid  by  the 
margarine  and  other  edible  fat  industries,  has  now  at  his  disposal  the 

*  Oil,  Paint  and  Drug  Rep.,  Feb.  2,  1914. 
t  Chem.  Ztg.,  37,  297. 


USES  OF  HYDROGENATED  OILS  161 

means  for  utilizing  lower  grade  materials  in  substitution  for  more 
costly  stock. 

By  hydrogenation,  oils  which  formerly  made  soaps  only  of  soft  con- 
sistency, now  yield  the  more  valuable  hard  soaps.  This  has  led  to  a 
very  rapid  development  of  the  art  with  respect  to  the  production  of 
soap-making  fats.  In  particular,  fish  and  whale  oils  have  been  made 
use  of,  because  these  oils  may  be  completely  deodorized  by  the  addi- 
tion of  hydrogen. 

According  to  a  Japanese  chemist,  Tsujimoto,  the  odor  of  fish  oil  is 
due  almost  entirely  to  a  fatty  constituent  and  not  to  so-called  impuri- 
ties. This  fatty  constituent  is  clupanodonic  acid  having  the  formula 
Ci8H2802,  which,  therefore,  by  the  addition  of  8  hydrogen  atoms, 
becomes  stearic  acid.  When  hydrogenated  down  to  an  iodine  num- 
ber of  about  50,  fish  oil  has  the  consistency  of  hard  tallow  and  the 
odor  of  fish  oil  is  wholly  absent.  Even  the  fishy  taste  is  scarcely  in 
evidence. 

For  soap  making  this  product  is  satisfactory  as  it  complies  with 
the  test  for  a  deodorized  fish  oil  suitable  for  soap  making  in  that  the 
odor  of  the  original  oil  is  not  apparent  when  ironing  laundered  goods 
on  which  such  soaps  are  used.  If,  however,  at  least  with  the  poorer 
grades  of  oil,  the  hydrogenation  is  not  carried  on  to  a  point  where 
the  iodine  number  is  approximately  50  or  less,  there  is  some  danger 
that  the  fishy  odor  will  become  apparent  during  the  ironing  operation. 

It  appears  not  improbable  that  unstable  odor-forming  nitrogenous 
impurities  in  fish  oil  add  hydrogen  during  the  hardening  process  and 
are  transformed  into  bodies  of  a  stable  character. 

Data  on  a  hydrogenating  plant  in  Norway  is  furnished  by  Commercial  Agent 
E.  W.  Thompson  of  the  Department  of  Commerce  (Consular  &  Trade  Reports, 
Jan.  14,  1914,  171)  who  reports  that  during  the  summer  of  1913  an  oil-hardening 
plant  was  opened  at  Fredrikstad  by  De  Nordiske  Fabriker,  with  head  office  at 
Christiania.  *  The  original  object  was  to  harden  whale  oil  for  the  soap  industry, 
but  as  the  result  of  experiments  with  edible  oils  the  plant  is  being  enlarged  to  a 
capacity  of  1000  barrels  a  day  with  the  expectation  of  hardening  cottonseed  and 
peanut  oils  for  the  margarine  makers.  If  this  plan  is  successful  it  may  double  the 

*  This  concern  is  said  to  be  a  German-Norwegian  company,  capitalized  at  about 
$833,500,  organized  to  work  a  new  German  method  of  hydrogenation.  The  Hafslund 
Falls  are  being  utilized  to  generate  the  electric  power  required  by  the  work  and  also 
to  manufacture  by  electrolysis  the  hydrogen  required  for  the  hardening  process  to 
which  the  purified  whale  oil  is  submitted  and  converted  into  a  solid  neutral  fat. 
The  daily  consumption  of  oil  is  about  300  barrels.  (Jour.  Ind.  and  Eng.  Chem. 
(1913),  608.)  The  hardened  fat  has  a  melting  point  between  40°  to  50°  C.  and 
is  stated  to  be  odorless  and  tasteless.  Although  at  the  present  time  principally 
used  for  soap  making,  in  all  probability  in  due  course  the  material  will  be  employed 
in  the  manufacture  of  edible  fats.  (Seifen.  Ztg.  (1913),  1413.) 


162  THE  HYDROGENATION  OF  OILS 

consumption  of  cottonseed  oil  in  the  margarine  industry.  The  Norwegian  firm 
will  purchase  the  best  grades  of  cottonseed  and  peanut  oils,  and  will  also  harden  on 
toll.  Many  European  margarine  factories  are  experimenting  on  hardened  cotton 
and  peanut  oils  to  replace  copra  oil,  which  is  high  in  price.* 

Some  criticism  has  been  directed  at  the  use  of  hardened  oils  at  least  for  edible 
purposes  on  the  ground  that  nickel  is  used  in  the  process,  but  the  manufacturers 
say  that  although  nickel  is  generally  used  none  of  it  is  left  in  the  oil,  and  that  even 
if  it  were  it  is  harmless,  as  shown  by  many  tests  with  animals  and  with  human 
"poison  squads." 

Samples  of  Norwegian  hydrogenated  whale  oil  which  have  come  to 
the  author's  attention  are  of  exceptionally  high  quality. 

Whale  oil  of  the  grades  known  as  0  and  1  hydrogenate  readily  with 
nickel  as  a  catalyzer.  No.  2  is  somewhat  more  difficult  and  No.  3 
is  decidedly  troublesome  to  treat  without  special  refining. 

Chinese  wood  or  tung  oil  may  be  rendered  very  hard  by  thorough  hydrogena- 
tion  and  the  product  often  shows  the  property  of  expanding  on  solidifying  from  a 
melted  state,  forming  a  friable  mass  instead  of  a  firm  block.  Hardened  linseed  oil 
sometimes  exhibits  a  like  behavior. 

Hardened  chrysalis  oil  is  described  by  Tsujimoto  (Jour.  Chem.  Ind.  Tokio,  1914, 
No.  191  and  Chem.  Ztg.  Rep.  1914,  110).  Hydrogenation  was  carried  out  with  a 
nickel  catalyzer  and  traces  of  nickel  were  found  in  the  ash  of  the  hardened  product. 

Soya  bean  oil  has  become  an  important  raw  material  for  hydrogenation  purposes. 
(Seifen.  Ztg.,  1914,  348.) 

The  commercial  side  of  fat  hardening  is  discussed  to  some  extent 
by  Schicht  t  and  the  value  of  fish  and  whale  oils  in  this  field  is  con- 
sidered. The  probable  place  hardened  fats  will  assume  in  the  soap 
and  edible  fat  industry  is  discussed  in  Seifensieder  Zeitung  (1913, 
768). 

In  this  country  very  little  has  as  yet  appeared  in  the  literature 
regarding  the  application  of  hydrogenated  oils  in  soap  making,  but 
in  Germany  considerable  space  has  been  given  by  the  trade  journals 
to  discussions  of  the  subject.  Some  of  the  statements  are  of  a  very 
contradictory  character  as  is,  of  course,  to  be  expected  in  the  early 
stages  of  development  of  this  important  subject,  especially  in  view 
of  the  very  considerable  degree  of  empiricism  which  prevails  in  some 
branches  of  the  soap-making  industry. 

It  is  to  be  regretted  that  so  much  of  the  published  matter  relates 
to  products  offered  under  trade  names  such  as  Talgol,  Candelite  and 

*  Hardened  sunflower  oil  is  mentioned  in  Seifensieder  Zeitung  (1913),  611.  The 
Knowles  Oxygen  Company,  of  Wolverhampton,  England,  has  contracted  with  the 
Sunlight  Soap  Factory,  in  Port  Arthur,  to  erect  an  annex  to  the  plant  for  the  pro- 
duction of  the  hydrogen  necessary  for  hardening  palm  oil;  the  oxygen  is  to  be  col- 
lected and  sold. 

t  Seifen.  Ztg.  (1913),  287. 


USES  OF  HYDROGENATED  OILS 


163 


similar  hydrogenated  fish  and  whale  oils,  etc.,  of  the  Germania  Oel- 
werke  at  Emmerich,  but  while  soap  making  as  practiced  in  Germany 
differs  in  several  respects  from  the  practice  in  this  country,  it  is  be- 
lieved the  work  abroad  will  prove  at  least  suggestive  if  not  instruc- 
tive.* 

In  the  following  an  attempt  has  been  made  to  briefly  review  the 
more  important  contributions  in  this  connection. 

Garth  f  states  that  fish  and  whale  oils  are  the  raw  materials  for  a 
considerable  proportion  of  the  hydrogenated  products  which,  up  to 
the  present  time,  have  found  application  in  soap  making.  Being 
relatively  low-priced  raw  material  many  attempts  have  been  made  to 
make  cheap  soaps  from  fish  oil.  These  attempts  in  the  past  have 
been  unproductive  because  the  objectionable  odor  reappears  after 
goods  are  laundered.  Hence  there  are  many  proposals  directed 
toward  the  production  of  odorless  fish  oil.  As  is  known  fish  oil  con- 
tains nitrogenous  compounds  and  certain  of  the  lower  fatty  acids 
arising  from  decomposition  of  the  fish  before  the  oil  is  expressed. 
Most  of  the  proposals  are  based  upon  the  assumption  that  these  sources 
of  the  evil  odor  can  be  removed  by  the  action  of  energetically-reacting 
bodies  such  as  sulfuric  acid  and  the  like.  However,  neither  treat- 
ment with  strong  acids  nor  distillation  with  superheated  steam  pro- 
duce unobjectionable  products.  By  hydrogenation  the  disagreeable 
odor  disappears;  nevertheless,  there  always  remains  an  odor  similar 
to  that  of  distilled  olein  which,  however,  is  completely  concealed  if 
the  product  is  worked  up  with  a  goodly  proportion  of  other  fats. 

Garth  t  observes  that  the  hydrogenated  fats  which  have  been 
used  in  the  soap  manufacture  appear  in  the  trade  as  Talgol,  Talgol 
extra,  Candelite,  Candelite  extra,  Crutolein,  Talgin,  etc.  Talgol 
has  a  melting  point  of  35°  to  37°  C.,  and  an  iodine  number  of  65  to 
70.  Talgol  extra  melts  at  42°  to  44°  C.  and  the  iodine  number  is 
45  to  55.  The  Candelite  products  are  harder,  Candelite  melting  at 

*  In  England  one  large  concern  is  offering  several  grades  of  hardened  fat  ranging 
as  follows: 


Iodine  No. 

M.P. 

Titer 

Al 

50 

40-42 

36 

A2 

85 

28-30 

32 

Cl 

60 

44-46 

45 

C2                                            

75 

35-37 

36 

t  Seifen.  Ztg.  (1912),  1278. 
t  Seifen.  Ztg.  (1912),  1279. 


164 


THE  HYDROGENATION  OF  OILS 


48°  to  50°  C.,  and  having  an  iodine  number  of  15  to  20,  while  Candelite 
extra  melts  at  50°  to  52°  C.  and  exhibits  an  iodine  number  of  5  to  10.* 
Heller  f  furnishes  the  following  data  on  these  products: 


Acid  No. 

Saponification 
No. 

Unsaponi- 
fiable 

Iodine 
No. 

Talgol  

3  5 

190  7 

0  33 

63  9 

Talgol  extra  
Candelite  

3.8 
3.8 

190.5 
190.4 

0.31 
0.41 

36.1 
18.4 

Candelite  extra  

4.4 

188.4 

0.52 

10.4 

FATTY  ACIDS 


Melting  point 

Titer 

Acid  No. 

Talgol 

38  5 

34  6 

199  7 

Talgol  extra  .  . 

45  5 

43.5 

199  9 

Candelite  
Candelite  extra  

48.5 
51.8 

47.4 
50.5 

198.9 
199.9 

Schaal  has  reported  J  the  results  of  his  observations  on  the  two 
products  Talgol  and  Candelite  derived  by  hydrogenation  of  fish  oil, 
etc.,  and  has  called  attention  to  the  adaptability  of  these  hardened 
fats  in  the  production  of  soap  base  or  milled  soap.  Both  Talgol  and 
Candelite  have  a  tallowy  appearance  with  this  difference,  that  one  is 
softer  and  one  is  harder  than  tallow.  At  first  glance  one  is  likely  to 
regard  these  fats  as  similar  to  high-grade  soap  tallow,  but  the  odor  of 
the  product  immediately  shows  this  is  not  the  case.  The  odor  is  not 
disagreeable  and  in  fact  resembles  some  grades  of  tallow.  It  is  sug- 
gestive of  the  cheesy  odor  given  off  by  tallow  which  has  been  stored 
for  a  considerable  time  in  warm  weather.  Of  the  two  products  Talgol 
and  Candelite,  the  odor  in  the  latter  is  less  noticeable. 

In  his  first  investigations  Schaal  simply  replaced  a  part  of  the  softer 
fats,  as  he  thought  Talgol  would  lose  its  firm  consistency  during  the 

*  The  Olwerke  Germania  has  trademarked  in  the  German  Patent  Office  the  words 
Andelite,  Candolit,  Cancellit,  Coryphol,  Doratol,  Dural,  Durettol,  Durolit,  Durotin, 
Durotal,  Duru,  Durutol,  Jutol,  Jutolin,  Kandel,  Kandelin,  Kandetil,  Kandorit, 
Kerzenit,  Kritolit,  Krunotin,  Krutello,  Krutol,  Krutolin,  Talgela,  Talgelin,  Talgol 
and  Urutol.  (Taschenkalender  f.  d.  Oel  und  Fett  Industrie,  1914.) 

t  Seifenfabrikant  (1912),  No.  31. 

t  The  results  of  investigations  by  Schaal  on  the  utilization  of  hardened  oils  in 
soap  manufacture  are  published  in  the  Seifensieder  Zeitung  (1912),  821,  846,  954 
and  979;  (1913),  173,  and  in  a  book  entitled  Die  Moderne  Toiletteseifen-Fabrikation, 
Augsburg,  1913,  to  which  reference  should  be  had  for  detailed  description. 


USES  OF  HYDROGENATED  OILS  165 

boiling  operation  and  would  return  to  a  consistency  approaching  that 
of  the  original  oil.  This  assumption  proved  to  be  unwarranted  as 
tests  with  small  samples  showed  that  the  Talgol  fatty  acids  were  as 
hard  as  the  Talgol  itself.  The  first  fat  mixture  used  for  preparing  a 
soap  consisted  of  the  following: 

40  parts  tallow. 
15  parts  Talgol. 
30  parts  bone  fat. 
15  parts  cocoanut  oil. 

No  rosin  was  used  as  it  was  desired  to  determine  the  influence  of 
the  Talgol  odor.  During  the  boiling  the  odor  of  Talgol  was  plainly 
in  evidence,  much  more  noticeable  in  fact  than  could  be  observed 
afterwards  in  the  finished  soap.  The  dried  curd  exhibited  a  wholly 
agreeable  odor  in  which  the  characteristic  odor  of  Talgol  could  not  be 
detected,  and  no  odor  was  in  evidence  of  a  nature  calculated  to  affect 
the  perfume.  The  soap  was  not  perfumed,  but  was  wrapped  in  paper 
and  laid  aside  a  few  weeks  for  further  observation.  In  another  trial 
the  tallow  was  reduced  and  the  Talgol  increased  in  amount,  the 
formula  being: 

25  parts  tallow. 

35  parts  Talgol. 

30  parts  bone  fat. 

10  parts  cocoanut  oil. 

The  saponification  progressed  satisfactorily,  indicating  that  Talgol 
readily  united  with  alkali.  As  the  bone  fat  employed  was  of  exception- 
ally dark  color,  the  soap  was  bleached  in  the  kettle  with  0.2  per  cent 
Blankit.  The  dried  product  had  a  fine  ivory  white  appearance,  but 
the  odor  of  Talgol  was  apparent  although  not  so  pronounced  as  to 
render  the  soap  unusable.  This  soap  base  milled  very  smoothly  and 
easily,  giving  an  excellent  finish.  In  another  trial  5  per  cent  of  rosin 
was  introduced  with  improvement  in  the  odor  of  the  soap  base. 

The  milled  and  perfumed  soap  was  kept  under  observation  and  it 
was  noted  that  some  perfumes  were  affected  by  the  Talgol  odor.  A 
person  with  a  keen  sense  of  smell  would  immediately  detect  the 
presence  of  Talgol.  Tests  were  conducted  with^a  number  of  perfumes* 
including  hyacinth,  lilac,  rose,  pathouly  and  violet,  each  cake  being 
separately  wrapped  in  parchment  paper.  It  was  found  that  the  two 
first-mentioned  perfumes  were  more  sensitive  to  the  presence  of  Tal- 
gol smell  and  gave  a  momentary  impression  that  the  soap  had  become 

*  Schaal  gives  a  number  of  perfume  formulae  for  hydrogenated  oil  soaps  in 
Seifen.  Ztg.  (1912),  979. 


166  THE  HYDROGENATION  OF  OILS 

rancid;  the  rose  was  slightly  affected  while  the  other  samples  were 
not  noticeably  changed.  Schaal  reaches  the  conclusion  that  the 
highest  grade  of  toilet  soap  perfumed  with  delicate  essential  oils  is 
affected  by  the  use  of  Talgol  or  Candelite  and  that  these  hardened 
oils  will  not  find  an  application  here.  Such  soaps  are,  however,  sold 
only  to  very  fastidious  trade  and  require  in  any  case  perfumes  of  the 
very  highest  grade.  On  the  other  hand,  in  manufacturing  ordinary 
grades  of  toilet  soap  which  are,  of  course,  made  in  enormous  quan- 
tities, up  to  about  35  per  cent  of  Talgol  or  Candelite  may  be  employed 
advantageously  in  the  fat  stock.  As  regards  solubility  in  water  and 
free  lathering  properties,  Schaal  found  Talgol  or  Candelite  to  afford 
satisfactory  results,  the  soaps  which  he  prepared  forming  a  lather 
immediately  which  was  thick  and  voluminous,  acting  in  fact  like  any 
standard  soap.  It  is  reported  that  the  Olwerke  Germania  has  been 
successful  in  producing  a  completely  odorless  product  at  a  somewhat 
higher  cost.  If  such  a  deodorized  product  can  be  put  out  at  reason- 
able price,  it  will  be  possible  to  make  toilet  soaps  of  the  highest  grade 
with  hardened  fats  derived  from  relatively  cheap  oils. 

Of  Talgol,  Schaal  notes  that  the  fat  is  readily  deprived  of  its  glycer- 
ine and  especially  well  by  the  Krebitz  process,*  and  soaps  made  from 
this  stock  are  prime  products. 

Schaal  states  that  so  long  as  these  hardened  fats  are  not  entirely 
odorless,  as  indicated  they  cannot  be  advanced  for  the  manufacture 
of  soap  stock  of  the  first  class.  For  these,  the  best  beef  tallow,  etc., 
must  remain  the  raw  material,  for  this  class  demands  the  best  that  the 
soap  industry  can  produce.  Talgol  is  therefore  considered  suitable 
only  for  working  up  into  soap  stock  of  second  and  third  grade.  In 
these  soaps  the  price  of  raw  material  plays  a  considerable  role,  and 
thus  Talgol  proves  an  advantageous  substitute  for  tallow.  Pure  Tal- 
gol soap  has  too  little  lathering  power  and  as  its  odor  is  also  objection- 
able it  is  not  advisable  to  allow  the  addition  of  Talgol  to  rise  above 
40  per  cent.  The  lathering  power  will  be  considerably  better  if  10  per 
cent  of  palm  kernel  or  cocoanut  oil  is  worked  in  and  the  solubility  of 
the  soap  is  also  much  increased.  If,  however,  60  per  cent  of  other  fats 
are  present,  bad  lathering  is  prevented,  and  the  product  meets  the  re- 
quirements of  the  trade.  The  yield  of  pure  salted  soap  on  the  average 
is  165  per  cent. 

The  following  are  some  recipes  given  by  Schaal  for  soap  stock  of  two 
grades. 

*  The  Krebitz  process  is  recommended  for  the  treatment  of  hardened  fats  in  the 
manufacture  of  toilet  soaps.  (Seifen.  Ztg.,  1914,  391.) 


USES  OF  HYDROGENATED  OILS  167 

Soap  Stock,  Second  Grade 

(1)   30  parts  Talgol  extra;  (2)   40  parts  Talgol  extra; 

40  parts  beef  tallow;  25  parts  beef  tallow; 

15  parts  peanut  or  corn  oil;  20  parts  peanut  or  corn  oil; 

15  parts  cocoanut  oil.  15  parts  cocoanut  oil. 

Soap  Stock,  Third  Grade 

(1)   40  parts  Talgol  extra;  (2)   40  parts  Talgol  extra; 

15  parts  beef  tallow;  30  parts  oleomargarine  waste, 

30  parts  oleomargarine  waste,  bone  fat,  hide  fat,  etc. ; 

bone  fat,  hide  fat,  etc.;  20  parts  bleached  palm  oil; 

10  parts  palm  kernel  oil  or  6  parts  cocoanut  oil; 

cocoanut  oil;  4  parts  rosin. 
5  parts  rosin. 

It  may  be  noted  that  with  each  increase  in  the  amount  of  Talgol, 
a  similar  increase  in  the  amount  of  softer  fats  is  demanded.  Talgol 
extra  is  a  rather  hard  fat  and  easily  permits  a  considerable  addition 
of  fluid  fats,  producing  a  pliable  plastic  soap  base  which  can  be  easily 
milled.  Talgol  like  tallow  is  saponifiable  with  some  difficulty  and 
for  the  complete  combination  of  it  with  alkali,  boiling  for  a  number  of 
hours  is  required.  The  boil  must  be  conducted  with  weak  lyes  of 
15  to  20  degrees  in  order  to  get  a  good  combination  of  fat  and  lye. 
With  respect  to  the  odor  of  the  soap  it  is  an  advantage  if  the  reaction 
between  the  fat  and  lye  is  extended  over  as  long  a  period  as  possible, 
since  the  odor  of  Talgol  thus  almost  completely  disappears.  When 
possible  the  Talgol  material  should  be  well  blown  with  steam  in  the 
kettles,  as  by  this  treatment  the  odor  is  almost  completely  removed. 

The  resulting  soap  base  displays  absolutely  no  difference  from  that 
of  a  straight  tallow  stock,  and  works  up  on  the  machines  exactly  as 
a  soap  from  beef  tallow;  indeed  it  may  be  said  that  milled  soap  from 
Talgol  has  a  finer,  cleaner  and  whiter  look  than  that  made  without 
it.  The  odor  may  be  permanently  concealed  in  finishing  the  soap 
by  means  of  appropriate  perfumes. 

The  tests  made  by  Schaal  of  Talgol  as  a  constituent  of  cold  process 
soaps  led  to  the  conclusion  that  it  only  has  value  in  combination  with 
cocoanut  oil.  The  saponification  of  Talgol  may  be  accomplished 
with  strong  tepid  lyes  if  the  following  conditions  are  observed.  First 
the  temperature  of  the  fat  at  the  moment  of  contact  with  the  lye 
must  be  at  least  50°  C.  and  on  cold  days  about  55°  C.  It  is  desirable 
to  warm  the  lye  to  25°  to  30°  C.  before  incorporating.  It  often 
happens  on  mixing  that  the  whole  mass  suddenly  solidifies  so  that  the 
mixture  must  be  warmed  to  liquefy.  Even  when  the  temperature 
of  the  bath  is  higher  than  the  figures  given,  solidification  takes  place 


168  THE  HYDROGENATION  OF  OILS 

on  running  in  the  cold  lye,  or  at  least  small  lumps  are  formed.  The 
union  of  the  fat  and  lye  takes  place  very  quickly;  the  mass  becomes 
solid  in  a  short  time  and  can  be  framed.  On  this  account  the  frames 
must  be  ready  at  hand.  In  the  frames  a  rather  strong  reaction  sets 
in,  and  heat  is  generated.  The  frames  should  be  well  covered  to 
take  advantage  of  this  rise  in  temperature.  The  finished  soap  is  very 
hard  and  almost  brittle  in  character  and  on  this  account  must  be  cut 
while  fresh.  It  has  a  fine  white  color,  but  is  not  transparent.  The 
odor  is  not  unpleasant,  and  varies  with  the  fat  used;  it  can  be  com- 
pletely covered  by  oil  of  citronella  or  lavender.  Artificial  oil  of  bitter 
almonds  is  less  adapted  to  permanently  cover  the  Talgol  odor. 
The  following  is  a  useful  formula : 

25  parts  Talgol, 

25  parts  Ceylon  cocoanut  oil, 

5  parts  castor  oil, 
28  parts  caustic  soda  lye,  37°  Be. 

The  mixture  of  fats  at  a  temperature  of  45°  to  50°  C.  is  stirred  well 
with  the  lye,  which  need  not  be  warmed.  In  about  one-half  hour 
reaction  is  under  way  and  the  product  should  at  once  be  framed.  If 
delayed  longer,  the  mass  becomes  almost  in  a  moment  solid  and  must 
be  warmed  to  soften.  This  is  unnecessary  if  the  frames  are  ready  at 
hand  as  above  cautioned.  This  soap  heats  up  strongly  in  the  frames 
and  on  cooling  is  plastic  with  a  somewhat  transparent  look.  It 
lathers  freely  like  a  shaving  soap  and  when  properly  perfumed  is  an 
excellent  product.  Such  a  soap  is  well  adapted  for  pressing,  which 
gives  it  a  fine  solid  appearance. 

For  cocoanut  oil  soaps  which  are  to  be  filled,  25  per  cent  of  Talgol 
is  recommended.  Such  soaps  cut  and  press  well  and  have  a  good 
solid  feel.  The  batch  should  be  maintained  at  a  temperature  of 
40°  C.  when  stirring,  lest  the  soap  get  too  solid  before  the  filling  is 
worked  in.  If  this  temperature  is  maintained  no  trouble  need  be 
feared  with  the  lye  or  the  filling.  In  weighing  off  the  oil  it  is  to  be 
noted  that  the  cocoanut  oil  should  be  first  introduced  and  then  the 
Talgol.  Otherwise  the  latter  sticks  to  the  side  of  the  kettle  and  the 
entire  mixture  then  has  to  be  made  hotter  than  is  necessary.  75  per 
cent  of  filling  can  be  incorporated  with  25  per  cent  of  Talgol,  giving 
a  yield  of  225  per  cent  without  danger  that  the  filling  will  settle  out 
or  fail  to  be  held  up.  The  soap  is  moulded  as  soon  as  thick  and  the 
moulds  left  covered  for  two  hours.  The  cooled  soap  is  hard  and 
tenacious  but  still  may  be  readily  pressed.  For  filling,  any  desired 
solution  of  salt,  potash  and  sugar  in  water  may  be  employed. 


USES  OF  HYDROGENATED  OILS  169 

The  following  is  an  appropriate  recipe  for  a  soap  of  this  class: 

22  \  kilos  Ceylon  cocoanut  oil, 
1\  kilos  Talgol, 

16|  kilos  caustic  soda  lye,  37°  Be., 
22£  kilos  filling  solution, 

perfumed  with  200  grams  of  oil  of  citronella  or  200  grams  of  lavender 
or  100  grams  of  each  oil. 

For  soaps  with  more  than  75  per  cent  filling  and  yields  of  250  per 
cent  and  over  it  is  best  to  conduct  the  process  in  the  warm  way. 

A  cold  process  shaving  soap  made  from  80  per  cent  Talgol  extra 
and  20  per  cent  cocoanut  oil  exhibited  satisfactory  lathering  prop- 
erties, but  in  spite  of  strong  perfuming  the  Talgol  odor  eventually 
reappeared,  especially  at  the  surface  of  the  cakes.* 

In  a  discussion  of  available  substitutes  for  palm  kernel  oil  f  it  is 
stated  that  hardened  fish  or  whale  oil  such  as  Talgol  cannot  be  used 
as  a  substitute  for  palm  kernel  oil.  The  peculiar  musty  odor  of  Tal- 
gol, which  to  be  sure  no  longer  resembles  that  of  the  original  oil,  is, 
however,  decidedly  penetrating.  Several  grades  of  soap  made  with 
Talgol  and  Crutolein  yielded  a  soap  of  too  pronounced  an  odor  to  be 
marketable.  Soap  containing  these  hardened  products  was  made  into 
a  soap  powder  and  although  the  percentage  of  the  hardened  fat  in 
this  product  was  low,  its  presence  was  still  detectable  by  the  odor. 
It  is,  however,  stated  that  if  means  can  be  found  for  the  removal  of 
this  characteristic  odor,  the  situation  as  regards  the  general  utility  of 
these  hardened  fats  will  be  entirely  altered. \ 

*  Weber,  Seifen.  Ztg.  (1913),  421. 

t  Seifen.  Ztg.  (1913),  312. 

t  Neither  tallow,  palm  kernel  or  cocoanut  oil  can  be  completely  substituted  in 
soap  making  by  hardened  fish  or  whale  oil,  but  the  latter  may  be  used  to  advantage 
as  an  addition  fat  in  laundry  soaps.  (Seifenfabrikant  (1913),  30;  Zeitsch.  f.  ang. 
Chem.  (1913),  310.) 

Leimdorfer  (Seifen.  Ztg.  (1913),  284  and  310)  treats  of  hardened  fats  with  special 
reference  to  the  soap  industry. 

The  addition  of  hardened  oil  to  other  soap  stocks  is  advantageous  for  lowering 
costs  and  gives  a  satisfactory  product  when  not  used  to  excess.  When  caustic 
potash  is  used  for  saponifying  a  mixture  of  65  per  cent  cottonseed  oil  and  35  per  cent 
Candelite  the  soap  does  not  grain  but  remains  clear.  (Seifenfabr.,  33,  30.) 

Hardened  oils  have  faced  several  problems.  The  technician  at  first  looked  upon 
them  with  distrust.  The  peculiar  odor  of  these  fats  has  caused  considerable  criti- 
cism and  their  surprisingly  white  color  has  been  looked  upon  as  unnatural.  The  soap 
produced  with  this  stock  has  a  characteristic  structure  and  its  appearance  changes 
somewhat  in  storage.  The  distrust  evidenced  toward  hydrogenated  fat  is  shown, 
however,  to  be  unjustified. 


170  THE  HYDROGENATION  OF  OILS 

Hardened  oils  when  used  in  soaps  *  in  the  proportion  of  50  to  80  per 
cent  give  products  which  are  very  hard,  dissolve  with  difficulty  and 
do  not  lather  readily.  The  saponification  is  also  said  to  be  somewhat 
slower  than  with  ordinary  soap  fats.  When  about  30  per  cent  of 
hardened  oil  is  used  the  soap  is  satisfactory. 

Semi-boiled  soaps  were  made  as  follows: 

(1)  50  parts  each  of  cocoanut  oil  and  hardened  oil  were  saponified 
at  80°  C.  with  38  degree  caustic  soda  lye.     The  lye  was  stirred  into 
the  hot  oil  mixture  and  the  kettle  kept  covered  until  a  well  saponified 
product  was  obtained.     A  little  alkali  was  added  to  show  a  faint  excess 
alkali  by  phenol  phthalein.     After  short  standing  the  soap  was  framed 
and  cooled.     It  had  a  fine  white  color,  but  possessed  a  sharp  odor 
(which  however  can   be  diminished  or  removed  by  boiling).     The 
lathering  qualities  appeared  less  pronounced  than  was  the  case  with 
a  soap  made  from  f  tallow  and  J  cocoanut  oil.     The  hardened  oil 
soap  dissolved  more  slowly  in  water,  f 

(2)  80  per  cent  hardened  oil  and  20  per  cent  cocoanut  oil  saponified 
in  the  same  way  was  very  hard  and  white  but  showed  no  lathering 
properties.     The  odor  was  slightly  rancid. 

(3)  30  per  cent  hardened  oil,  25  per  cent  peanut  oil,  30  per  cent 
cocoanut  oil  and  15  per  cent  rosin  showed  a  rate  of  saponification 
which  was  normal;  the  soap  was  yellowish,  the  odor  and  solubility 
satisfactory,  but  the  lathering  properties  were  not  quite  as  good  as 
normal  soap. 

The  conclusion  reached  with  the  hardened  oils  tested  was  that  very 
hard  soaps  could  be  produced  which  would  show  great  economy  in 
use,  that  they  gave  a  poorer  lather,  that  there  was  some  odor  over 
and  above  that  resulting  in  use  of  tallow,  and  that  the  saponification 
was  slightly  slower.  J  Hardened  oils  were  also  found  to  give  dark 

An  example  of  a  satisfactory  soap  base  for  toilet  soaps  is  given  in  the  following 

formula:  15  parts  cocoanut  oil, 

45  parts  tallow  oil, 
40  parts  Talgol, 

and  suggestions  are  made  for  the  manufacture  of  laundry  soaps,  white-grained 
soaps,  cold  process  soaps,  transparent  glycerine  soaps,  soap  powder,  etc.  The 
hardened  fat  is  not  suitable  for  the  production  of  transparent  soft  soaps  or  natural 
grain  soaps.  (Seifenfabrikant  (1912),  1229,  1257.) 

*  Seifen.  Ztg.  (1912),  660. 

t  Weber  (Seifen.  Ztg.  (1913),  421)  gives  a  somewhat  complicated  procedure  for 
making  soap  base  with  hardened  oils  of  the  Talgol  type. 

t  Leimdorfer  (J.  S.  C.  I.,  1914,  206)  states  that  the  speed  of  saponification  of 
hydrogenated  fats  is  greater  than  the  analogous  natural  fat  (tallow)  under  similar 
conditions. 


USES  OF  HYDROGENATED  OILS  171 

fatty  acids  by  the  Twitchell  process  and  odor  of  the  fatty  acids  was 
not  regarded  as  entirely  satisfactory. 

A  procedure  for  making  milled  soap  base  from  hardened  oil  *  in- 
volves the  formula: 

1200  pounds  Talgol  extra, 
1200  pounds  beef  tallow, 
600  pounds  Ceylon  cocoanut  oil. 

The  tallow  first  was  placed  in  the  kettle  and  saponified  with  20 
degree  caustic  soda  lye  somewhat  diluted  with  water.  A  little  salt 
was  added  at  the  beginning  of  the  boiling  to  prevent  lumpiness.  The 
Talgol  extra  was  then  added  and  saponified.  This  addition  gave  the 
stock  a  different  odor  which,  however,  diminished  as  the  operation 
progressed  and  the  final  product  possessed  the  desired  odor  of  good 
neutral  soap.  After  slow  boiling  for  several  hours  the  stock  was 
allowed  to  stand  over  night  after  it  had  been  ascertained  that  a 
sufficient  excess  of  alkali  was  present.  Subsequently  the  soap  was 
salted  out  with  24  degree  brine,  and  after  settling  the  spent  lye  was 
replaced  with  8  degree  caustic  soda  lye.  Slow  boiling  was  continued 
for  several  hours  to  complete  the  saponification  and  improve  the  odor. 
After  settling  over  night  the  lye  was  removed  and  the  cocoanut  oil, 
with  the  required  amount  of  30  degree  caustic  soda  lye,  was  introduced. 
Less  caustic  soda  was  needed  than  the  calculated  amount  for  the  cocoa- 
nut  oil  employed  as  the  saponified  stock  contained  some  entrained 
lye.  A  small  quantity  of  weak  brine  was  added  and  boiling  continued 
for  several  hours.  Strong  brine  was  then  introduced  to  salt  out  the 
saponified  product.  After  standing  36  hours  the  stock  was  withdrawn, 
solidified  in  cooling  apparatus  and  subsequently  dried.  A  relatively 
low  temperature  was  used  in  drying  yet  no  difficulty  was  experienced 
in  securing  a  rapid  removal  of  the  moisture.  The  addition  of  hydro- 
genated  oil  to  soft  fats  prevents  adhesion  of  the  resulting  soap  in  the 
drying  apparatus. 

The  soap  base  machined  perfectly  and  yielded  a  first-class  finished 
product.  Samples  of  the  soap  were  stored  for  several  months  and 
then  given  to  unbiased  persons  for  criticism  without  informing  these 
judges  that  hydrogenated  oil  had  been  used  in  the  make-up  of  the 
soap.  All  united  in  declaring  the  product  an  excellent  one  and 
the  freshness  of  the  perfume  was  noted.  The  lather  exhibited  by  the 
milled  soap  was  of  a  good  stiff  consistency  and  quite  lasting,  resembling 
that  afforded  by  a  shaving  soap. 

On  examination,  the  glycerine-containing  lyes  derived  in  the  fore- 

*  Seifen.  Ztg.  (1913),  334  and  368. 


172  THE  HYDROGENATION  OF  OILS 

going  method  of  saponification  were  found  to  resemble  those  obtained 
when  beef  tallow  was  used  without  additions  of  the  hydrogenated 
fat. 

Garth  *  states  that  a  grained  soap  having  a  desirable  hard  feel  may 
be  obtained  by  the  use  of  Talgol,  as  has  been  proven  by  practical 
experience.  Also  a  larger  yield  is  obtained,  and  since  the  Talgol 
products  are  cheaper  than  tallow  itself,  a  double  advantage  is  secured. 
The  hydrogenated  fat  finds  application  not  only  in  textile  and  laundry 
soaps  but  also  in  soap  base  intended  for  toilet  soap  manufacture. 
By  itself  Talgol  is  seldom  used.  In  the  case  of  laundry  soap  25  to 
30  per  cent  of  rosin  should  be  employed.  As  to  shaving  and  trans- 
parent glycerine  soaps,  see  Seifen.  Ztg.  (1913),  954.  Too  large  an 
addition  of  the  Talgol  to  grained  soap  causes  the  framed  soap  to  check 
badly  on  standing. 

Bergo  t  criticizes  hardened  oil  from  the  point  of  view  of  soap  making, 
stating  that  only  a  very  moderate  percentage  of  the  hardened  oil  in 
conjunction  with  other  oils  and  fats  can  be  used,  otherwise  the  lather- 
ing quality  of  the  soap  is  seriously  influenced.  The  somewhat  musty 
odor  which  soaps  containing  30  per  cent  or  more  hardened  oil  show, 
may  be  diminished  or  eliminated  through  long  boiling,  or  by  repeated 
washing,  or  by  the  addition  of  a  suitable  perfuming  agent;  but  long 
boiling,  as  well  as  repeated  salting  out  or  covering  the  odor  with  per- 
fumes, is  costly.  Another  objection,  namely,  that  soaps  made  with 
additions  of  hardened  oil  lose  in  lathering  quality,  is  a  more  important 
consideration  than  the  odor.  The  consumer  looks  upon  good  solu- 
bility and  strong  lathering  properties  as  essential  in  soaps.  Bergo 
thinks  if  success  is  not  attained  in  removing  this  objectionable  feature, 
the  application  of  hydrogenated  oils  in  the  soap  industry  will  remain 
very  limited. 

A  further  obstacle  on  a  large  scale  is  the  color  of  the  product  ob- 
tained by  autoclave  saponification.  Hardened  oil,  which  as  a  neutral 
fat  shows  a  beautiful  white  color,  gives  fatty  acids  which  in  spite  of 
all  possible  precautions  in  the  autoclave  treatment  and  even  with  the 
use  of  bleaching  material,  such  as  decrolin  and  the  like,  appear  of  a 
yellow  color  and  in  consequence  are  not  suitable  for  white  soaps.  If, 
he  states,  we  do  not  saponify  these  oils  for  fatty  acids,  but  process 
them  as  neutral  fats  and  saponify  with  caustic  alkali,  then  the  differ- 
ence in  price  as  compared  with  other  available  fats  and  oils  is  so  far 
reduced  that  it  is  a  question  whether  the  soap  manufacturer  will  use 
such  artificially  hardened  oils  and  thereby  reduce  the  quality  of  the 

*  Seifen.  Ztg.  (1912),  1279. 
t  Seifen.  Ztg.  (1912),  1333. 


USES  OF  HYDROGENATED  OILS  173 

soap.  The  hopes  of  the  soap  maker  have  been  based  on  the  supposition 
that  a  fat  which  would  be  a  substitute  in  the  manufacture  of  white 
grain  soaps  would  be  found,  because  the  fats  and  oils  now  available 
for  making  white  soaps  are  very  few;  while  for  yellow  soaps  a  whole 
series  of  fats  are  obtainable  and  these  Bergo  regards  as  practically 
no  more  costly  than  hardened  oil  costs  to-day.  Hence  he  thinks  these 
new  raw  materials  offer  no  advantage  for  the  soap  industry  in  Ger- 
many on  account  of  their  price  and  defects  mentioned.* 

In  contrast  to  the  views  of  Bergo,  a  writer  in  Seifen.  Ztg.  (1912),  101, 
refers  to  the  comment  that  hydrogenated  fish  oil  gives  dark  unsightly 
soaps  which  do  not  show  good  lathering  properties,  and  asserts  that 
hardened  animal  and  vegetable  oils  after  careful  boiling  give  soaps 
which  not  only  are  harder  than  those  from  the  original  oil,  but  are 
essentially  whiter.  If  dark  soaps  have  been  produced,  one  perhaps 
can  explain  the  failure  on  the  ground  that  nickel  soaps  were  present 
in  the  hardened  oil  and  through  sulfur  compounds  in  the  lye  were 
converted  into  sulfide  of  nickel.  The  lack  of  lathering  qualities 
of  soap  made  from  hardened  fish  or  whale  oil  he  contends  is  a  per- 
fectly natural  result.  Hardened  fish  oil  finds  its  analogue  in  tallow. 
Pure  tallow  soaps  are  only  indifferently  soluble  and  lather  poorly; 
hence  this  condition  is  to  be  expected  in  hardened  fish  oil. 

Among  a  large  collection  of  samples  of  soaps  made  from  various 
hardened  oils,  including  many  marine  animal  oils,  some  were  found 
to  have  a  disagreeable  odor  like  oil  which  has  been  distilled.  This 
penetrating  odor,  which  in  distillation  plants  arises  through  partial 
decomposition  of  fatty  bodies,  is  regarded  as  due  to  acrolein  and  is 
not  a  necessary  consequence  of  hydrogenation,  but  is  simply  a  result 
of  over-heating  the  oil  at  some  time  during  operation.  In  carrying 
out  the  process  technically,  too  high  a  temperature  should  be  avoided, 
thus  eliminating  the  disagreeable  odor  and  producing  a  hardened  oil 
from  which  soap  of  high  quality  may  be  prepared.  By  the  addition 
to  hardened  fish  or  vegetable  oil  of  other  fatty  material,  such  as  palm 

*  It  should  be  remembered  that  in  Germany  the  Leprince  and  Siveke  Patent 
141,029  is  generally  regarded  as  controlling,  and  is  in  strong  hands.  In  consequence 
the  criticism  of  hardened  oil  products  by  professional  circles  has  been  perhaps  unduly 
severe,  if  not  in  part  unwarranted. 

Haleco  (Seifen.  Ztg.  (1913),  16)  feels  that  the  stand  taken  by  Bergo  is  unwar- 
ranted, because  although  the  hardening  of  oils  on  a  large  scale  has  been  in  practical 
operation  for  only  a  short  period,  yet  in  that  time  there  has  been  a  very  considerable 
demand  for  the  hardened  material,  which  demand  is  daily  increasing  in  the  soap 
industry  and  other  fields.  To-day  soaps  of  various  qualities,  including  fine  toilet 
soaps,  are  being  made  with  a  considerable  proportion  of  hardened  oil  which  shows 
that  the  new  material  offers  advantages. 


174  THE   HYDROGENATION  OF  OILS 

kernel  or  cocoanut  oil  and  rosin,  a  quick  lathering  soap  may  be  pre- 
pared which  satisfies  all  requirements. 

Hauser  *  is  of  the  view  that  the  application  of  hardened  oils  in  soap 
making  is  for  the  time  considerably  limited.  It  is  not  impossible 
that  a  considerable  simplification  of  the  apparatus  will  enable  the  soap 
manufacturers  to  make  use  of  it  more  extensively.  The  more  impor- 
tant applications,  to  Hauser,  appear  to  be  in  the  stearin  and  edible  fat 
industry.  He  regards  the  soaps  made  from  hardened  fat  as  lacking 
in  satisfactory  texture  and  emulsifying  properties,  as  not  exhibiting 
the  best  of  keeping  qualities  and  in  storage  sometimes  even  develop- 
ing an  undesirable  odor.  Then,  too,  he  considers  the  yield  of  glycer- 
ine to  be  unfavorably  affected  by  hydrogenation  and  the  fatty  acids 
of  hardened  oil  to  be  darker  than  those  of  the  normal  oil.  In  a  modern 
soap  establishment  it  is  recommended  that  cheap,  low-grade  fat  stock 
be  the  raw  material,  which,  after  purification,  is  split  and  the  result- 
ing fatty  acids  are  distilled  after  hardening  by  treatment  with  sulfuric 
acid.  In  this  way  with  great  simplicity  and  certainty,  according  to 
Hauser,  fractions  of  any  desired  titer  may  be  obtained  for  various 
soap  compositions  without  the  occurrence  of  undesirable  side  reac- 
tions which  he  apparently  thinks  are  unavoidable  in  hydrogenation 
processes.! 

kln  the  stearin  industry  the  oil  may  be  hardened  and  then  saponified, 
or  the  glycerine  first  may  be  removed  and  the  fatty  acids  hardened. 
It  no  longer  becomes  necessary  to  employ  complicated  pressing  oper- 
ations to  separate  stearin  from  olein  as  the  stearin  may  be  di- 

*  Seifen.  Ztg.  (1913),  141. 

t  Favorable  comment  of  the  Germania  Oelwerke  products  is  made  by  "R.  D." 
(Seifen.  Ztg.  (1912),  517)  who  states  that  these  hardened  oils  have  many  technical 
uses.  In  soap  making  they  are  used  to  advantage  and  give  a  good  product.  Talgol 
and  Talgol  extra  are  used  as  entire  substitutes  for  tallow.  Talgol  is  best  for  common 
household  soaps,  Talgol  extra  for  toilet  soaps.  Candelite  and  Candelite  extra  on 
account  of  high  melting  point  find  advantageous  application  in  the  stearin  and 
candle  industry.  He  considers  the  odor  of  the  hardened  oils  as  slight  and  unob- 
jectionable. The  color  is  gray-yellow.  Soaps  made  from  these  correspond  to  the 
trade  requirements.  Toilet  soaps  have  a  pure  white  color  and  do  not  darken  or 
discolor  on  standing,  and  the  perfume  remains  intact.  Lower-grade  soaps  possess 
a  satisfactory  appearance,  lather  well  and  are  sufficiently  firm  and  the  odor  is  satis- 
factory. 

Considering  the  application  of  hardened  fat  in  soap  making  Schuck  (Soap 
Gazette  and  Perfumer,  1914,  55)  states  that  on  account  of  the  high  titer  of  the  fat 
it  is  not  advisable,  in  fact  well  nigh  impossible,  to  make  a  settled  soap  (without 
rosin)  from  the  hydrogenated  product  alone.  Such  a  soap  would  be  too  brittle, 
would  crack  and  would  not  lather  at  all. 

Train  oil  (hardened)  as  a  competitor  of  tallow  is  considered  in  Soap  Gazette  and 
Perfumer,  1913,  222.  See  also  article  by  Heller,  ibid.,  1913,  263. 


USES  OF  HYDROGENATED  OILS 


175 


rectly  obtained.     The  products  to  which  he  refers  have  the  following 
constants : 


Talgol 

Talgol  extra 

Candelite 

Candelite 
extra 

Iodine  number 

65-70 

45-55 

15-20 

5-10 

Melting  point  
Saponification  value  

35-37°  C. 
192 

42-45°  C. 
192 

48-50°  C. 
192 

50-52 
192 

Unsaponifiable  

under  1% 

under  1% 

under  1% 

under  1% 

Glycerine  content  

9-10% 

9-10 

9-10 

9-10 

A  polemical  article  by  Ribot  *  denounces  the  proposal  to  use  har- 
dened fish  or  whale  oil,  no  matter  how  well  refined,  in  the  best  grade 
of  toilet  soaps.  Furthermore  he  does  not  consider  such  hardened 
oils  to  be  substitute  fats  for  tallow  or  palm  kernel  oil,  but  rather  that 
the  former  may  be  employed  as  addition  or  filling-in  fat  stock.  20  to 
25  per  cent  may  be  added  to  a  cheap  toilet  soap  base  without  detri- 
ment; 30  per  cent  or  even  40  per  cent  may  be  employed  in  laundry 
soaps.  In  white  soft  soaps  40  to  50  per  cent  of  Crutolin  may  be  used.f 
Schaal  |  apparently  is  in  agreement  with  Ribot  that  for  the  highest 
grade  of  toilet  soap  base,  tallow  should  not  be  materially  reduced  or 
displaced  by  Talgol,  but' maintains  that  a  soap  base  may  be  prepared 
with  35  to  40  per  cent  of  Talgol  which  yields  a  handsome  milled  soap 
permanent  in  quality  and  suffering  no  eventual  change  in  color.  He 
also  asserts  that  for  ordinary  toilet  soap  base  Talgol  is  in  no  sense  an 
addition  or  filling-in  fat,  but  is  a  real  substitute  for  tallow,  and  that 
the  same  is  true  of  Talgol  extra  and  Candelite  respectively  for  shaving 
soaps  and  glycerine  transparent  soaps;  further  that  the  hydrogen- 
ation  process  is  an  important  and  fruitful  discovery  for  the  soap 
industry,  especially  for  toilet  soap  manufacture. 

In  "Eschweger"  soaps  tallow  may  be  completely  replaced  by  Tal- 
gol,! which  produces  a  firmer  soap;  the  yield  is  good  and  the  odor 
satisfactory  and  no  objection  has  been  raised  to  its  lathering  qualities. 

*  Seifen.  Ztg.  (1913),  142. 

t  In  response  to  Ribot  an  article  appeared  in  Seifensieder  Zeitung  (1913),  173, 
by  Schaal  in  which  the  latter  makes  clear  that  he  did  not  propose  hydrogenated 
fish  or  whale  oil  of  the  Talgol  type  for  making  the  very  highest  grade  of  soap  base; 
he  recommends  such  fats  particularly  for  toilet  soaps  of  medium  quality.  Schaal 
also  states  that  he  has  never  recommended  complete  substitution  of  tallow  by  Talgol 
fat  in  the  highest  grade  of  toilet  soap  base  and  calls  attention  to  the  formulae  which 
he  has  published  in  the  past  in  which  a  substantial  amount  of  tallow  is  specified. 

t  Seifen.  Ztg.  (1913),  173. 

§  Seifen.  Ztg.  (1912),  1230. 


176  THE  HYDROGENATION  OF  OILS 

Two  formulae  are  given  for  filled  Eschweger  soap  according  to  which 
a  firm  marbled  product  is  obtained.* 

Transparent  glycerine  soaps  may  be  prepared  by  the  use  of  a  hard 
variety  of  hardened  oil,  Candelite  being  especially  suitable,  and  with 
this  material  a  soap  of  very  satisfactory  transparent  appearance  and 
firm  consistency  may  be  prepared  without  using  more  than  a  normal 
amount  of  alcohol.  The  following  are  suitable  formulas  for  the  prep- 
aration of  such  soaps: 

Cheap  Grade 

90  kilos  Candelite. 

90  kilos  Ceylon  cocoanut  oil. 

84  kilos  castor  oil. 
144  kilos  caustic  soda  lye,  38°  B6. 

90  kilos  sugar  dissolved  in  an  equal  weight  of  water. 
100  kilos  soap  filling. 

30  kilos  soda  crystals. 
Alcohol  q.s. 

The  soap  filling  consists  of  100  parts  salt,  140  parts  potash,  40  parts 
sugar  and  sufficient  water  to  produce  a  solution  of  21°  Be. 

Belter  Grade 

90  kilos  Candelite. 
120  kilos  Ceylon  cocoanut  oil. 

90  kilos  castor  oil. 
166  kilos  caustic  soda  lye,  38°  Be*. 
100  kilos  sugar  dissolved  in  75  kilos  of  water. 

40  kilos  soap  filling. 

10  kilos  glycerine. 
Alcohol  q.s. 

The  Candelite  should  first  be  melted,  the  cocoanut  oil  then  added 
and  finally  the  castor  oil  introduced.  Saponification  is  carried  out 
by  the  self-heating  method,  it  being  desirable  to  allow  the  saponified 
mass  to  stand  an  hour  or  so  in  order  to  assure  a  complete  union  of  the 

*  "Eschweger"  is  a  marbled  soap,  made  by  saponifying  tallow  and  soft  fats 
together  with  about  one-third  of  their  weight,  or  more,  of  cocoanut  oil.  The  quan- 
tity of  lye  is  gauged  so  as  to  have  the  soap  very  nearly  neutral  at  the  end  of  the 
operation,  as  there  is  no  separation  of  waste  lye.  All  that  goes  into  the  kettle  also 
goes  into  the  soap  except  of  course  water  removed  by  evaporation.  Owing  to 
the  properties  of  cocoanut  oil,  such  soap,  in  absorbing  a  considerable  amount  of 
salt  solution,  becomes  of  a  peculiar  consistency,  while  hot,  and  crystallization  ensues 
with  the  formation  of  "marble"  or  "mottle"  on  cooling  in  the  frame.  At  the  same 
time  the  soap  holds  much  more  water  than  one  which  has  been  mottled  by  boiling 
down  a  soap  made  entirely  of  soft  fats. 


USES  OF  HYDROGENATED  OILS  177 

ingredients.  Then  the  sugar  solution  and  filling  are  added.  By 
proceeding  in  this  manner  a  clear  product  is  obtained  which  does  not 
subsequently  darken  in  storage.  The  amount  of  alcohol  is  usually 
about  3  to  4  per  cent,  calculated  on  the  soap  material.  For  the  better 
quality  a  very  satisfactory  perfuming  composition  is  obtained  by 
mixing  equal  parts  of  "  palma  rosa  "  oil  and  artificial  geranium  oil 
using  1500  grams  to  the  formula  given  above.  For  the  cheaper  grade 
of  soap  a  good  perfuming  agent  consists  of  a  mixture  of  equal  parts  of 
Java  citronella  oil  and  benzyl  acetate.  2000  grams  of  this  mixture 
should  be  used  for  the  amount  of  material  specified  in  the  formula 
first  above  given.* 

Hardened  oil  is  advantageously  used  in  shaving  soaps  according 
to  Schaal.f  A  formula  given  by  him  is  the  following: 

50  kilos  Talgol  extra. 

10  kilos  Ceylon  cocoanut  oil. 

10  kilos  lard. 

20  kilos  caustic  soda  lye,  38°  Be". 

21  kilos  caustic  potash  lye,  37°  Be". 

The  mixing  takes  place  at  a  temperature  of  52°  C.  The  lyes  are 
first  mixed  and  then  added  in  a  thin  even  stream,  stirring  well  mean- 
while in  order  to  quickly  get  a  thorough  incorporation.  After  J  to  J 
hour  the  batch  stirs  thickly  and  should  be  promptly  framed.  The 
mass  heats  strongly  in  the  frames  and  to  take  advantage  of  this  the 
frames  should  be  covered  with  bagging.  By  such  treatment  a  section 
of  the  soap  will  show  a  uniform  texture  from  center  to  edge. 

If  it  is  preferred  to  prepare  this  soap  by  the  warm  process,  it  is 
necessary  to  add  5  kilos  of  potash  solution  of  12°  B6.  to  the  caustic 
lyes  and  to  prolong  the  stirring  until  the  mass  has  the  proper  body; 
the  kettle  is  then  well  covered  and  its  contents  given  time  to  react. 
After  2  to  3  hours  spontaneous  heating  will  have  set  in.  The  kettle 
is  again  opened,  the  contents  well  crutched,  until  uniform,  and  at  the 
same  time  perfume  can  be  worked  in.  The  soap  is  now  ready  for 
framing,  but  the  frames  need  not  be  covered.  The  potash  solution 
is  added  to  keep  the  soap  sufficiently  fluid  to  permit  of  crutching. 
Without  this  addition  the  soap  would  be  so  solid  and  tenacious  that 
the  crutch  could  scarcely  operate.  The  finished  soap  has  a  flawless 
appearance,  is  almost  white,  fairly  solid  and  handles  well  in  cutting 
and  packing. 

*  Schaal,  Seifen.  Ztg.  (1912),  955. 

t  Seifen.  Ztg.  (1912),  954,  and  Die  Moderne  Toiletteseifen-Fabrikation. 


178  THE  HYDROGENATION  OF  OILS 

A  perfume  composition  which  may  be  employed  in  this  soap  con- 
sists of  the  following : 

200  grams  oil  of  rosemary. 

200  grams  oil  of  bitter  almonds  (artificial). 

150  grams  oil  of  lavender. 

75  grams  oil  of  thyme  (white). 
100  grams  oil  of  sassafras. 

25  grams  oil  of  wintergreen  (artificial). 

The  odor  and  lathering  properties  of  soaps  made  from  hydrogen- 
ated  oil  are  discussed  by  Garth  *  who  considers  the  characteristic 
odor  of  hardened  oils  of  the  Talgol  type  to  be  in  nowise  disagree- 
able. In  laundry  soaps  the  aromatic  odor  of  the  rosin  overcomes  the 
Talgol  smell.  In  making  toilet  soaps  one  has  to  take  greater  care 
that  the  Talgol  addition  is  well  gauged  as  otherwise  the  proportion 
of  the  customary  perfuming  agents  has  to  be  varied.  With  regard 
to  the  diminution  of  the  lathering  power  he  states  that  soaps  from 
pure  Talgol  have  almost  no  lather,  and  in  this  connection  refers  to 
the  interesting  work  of  Krafft  and  other  investigators  who  have  shown 
that  the  detergent  action  of  soap  is  dependent  upon  the  nature  of  the 
fatty  acid,  and  that  there  exists  an  important  difference  in  operation 
between  stearin  and  olein  soaps.  Soaps  from  palmitin  or  stearin 
at  common  temperature  are  unworkable  and  develop  their  detergent 
or  emulsion-forming  properties  only  when  a  temperature  is  reached 
which  is  approximately  that  of  the  melting  point  of  their  fatty  acids. 
On  the  other  hand  the  olein  soaps  are  soluble  at  ordinary  temper- 
atures thus  exerting  detergent  action  at  low  temperatures,  but  at  a 
temperature  of  about  80°  C.  they  lose  their  emulsion-forming  qualities. 
Thus  it  will  be  seen  why  soaps  made  from  pure  tallow,  or  hardened 
fat,  exert  a  very  slight  detergent  action  at  ordinary  temperature.  In 
working  with  hardened  fat  the  soap  expert  should  take  cognizance 
of  the  manner  in  which  the  soap  is  to  be  used  and  employ  such  mate- 
rials as  give  the  desired  detergent  property  under  these  conditions. 

With  30  to  35  per  cent  of  hydrogenated  oil  of  the  Talgol  type, 
Weber  f  has  made  a  satisfactory  soap  base  holding  its  perfume  well, 
and  although  prepared  without  special  manipulation  did  not,  after 
standing  for  half  a  year,  show  the  hardened  oil  odor  when  broken. 
This  interval  of  time  is  sufficient  to  determine  with  certainty  whether 
or  not  the  characteristic  odor  can  be  permanently  suppressed. 

The  fatty  acids  of  hydrogenated  oil  have  been  examined  by  Luksck  J 

*  Seifen.  Ztg.  (1912),  1309. 

t  Seifen.  Ztg.  (1913),  421. 

t  Seifen.  Ztg.  (1912),  718  and  742. 


USES  OF  HYDROGENATED  OILS  179 

with  reference  to  their  applicability  as  candle  material.  A  product 
having  a  titer  of  about  60  was  observed  to  have  a  greasy  feel,  to  be  of 
amorphous  texture  and  to  be  lacking  in  ring  and  transparency.  So 
far  as  the  samples  examined  by  Luksch  are  concerned  the  product  does 
not  appear  to  be  suitable  as  a  candle  material  without  considerable 
compounding.* 

In  saponifying  for  fatty  acids  it  is  not  advisable  to  run  above  92  per 
cent,  as  otherwise  the  fatty  acids  are  likely  to  be  dark  and  the  result- 
ing soap  off  color.  When  hydrogenated  fish  oil  has  been  split  the  fatty 
acids  are  saponified  in  the  customary  way  by  carbonated  alkali. 
In  finishing,  the  soap  should  not  be  too  thin;  otherwise,  in  spite  of 
the  high  melting  point  of  the  hardened  fat,  the  soap  will  be  soft. 
The  soap  should  be  separated  only  with  an  excess  of  lye.  It  separates 
rather  badly  and  should  be  allowed  to  stand  two  or  three  days  in  the 
kettle  in  order  to  harden.  A  soap  made  from  Talgol  with  30  per  cent 
of  rosin  is  of  fair  appearance,  lacking,  however,  the  transparency  of 
soap  prepared  with  a  large  content  of  palm  kernel  oil.  While  the  color 
is  good,  there  is  a  noticeable  dullness  of  surface.  After  drying  and 
pressing  it  acquires  a  satisfactory  glossy  finish.  While  a  soap  made 
only  from  hardened  fish  or  whale  oil  has  practically  no  lathering  prop- 
erties, the  addition  of  30  per  cent  of  rosin  greatly  improves  this  defect 
and  very  good  lathering  properties  result. f 

*  Even  if  it  were  possible,  "J.  G."  states  (Seifen.  Ztg.  (1912),  1146),  to  split  the 
fat  completely  on  a  commercial  scale,  the  color  of  the  fatty  acids  excludes  the  direct 
application  of  the  product  in  candle  manufacture.  He  even  claims  that  it  is  neces- 
sary to  subject  the  saponified  product  either  to  distillation  or  to  pressing,  and  that 
in  the  latter  case  the  poor  crystallization  of  the  fatty  acids  gives  rise  to  difficulties. 
But  he  adds  that  the  ordinary  stearin  candle  is  made  up  largely  of  a  mixture  of 
palmitic  and  stearic  acid  in  which  a  certain  ratio  between  the  two  fatty  acids  must 
exist  to  maintain  the  quality  of  the  candle.  Hence  in  judging  hardened  fat  with 
reference  to  its  application  as  a  candle  material,  the  composition  of  the  original 
fat  is  not  unimportant,  for  useful  mixtures  may  well  be  obtained  through  careful 
selection  of  the  raw  materials.  In  those  cases  where  the  nature  of  the  chemical 
individuals  derived  by  hydrogenation  have  not  been  entirely  made  clear,  as  in  the 
case  of  fish  and  whale  oil,  further  practical  investigations  will  be  necessary  to  show 
whether  or  not  hydrogenation  will  afford  a  generally  useful  product  in  candle  manu- 
facture. 

t  Seifen.  Ztg.  (1912),  870. 

A  few  years  hence  when  oil  hydrogenation  has  found  its  measure  arid  the  more 
important  points  concerning  it  have  reached  definite  settlement,  the  allotment  of 
space  to  a  number  of  the  discussions  appearing  in  this  chapter  hardly  would  be 
warranted,  but  at  the  present  time  when  many  are  desirous  of  having  at  hand  a 
review  which  comprises  all  or  nearly  all  the  published  work  to  date,  containing 
though  it  does  a  considerable  divergency  of  opinion,  there  appears  ample  justification 
for  the  inclusion  of  such  discussions  as  those  given  above. 


180  THE  HYDROGENATION  OF  OILS 

A  tallow-like  product  which  has  been  brought  into  the  market  as 
"  Talgit "  is  prepared  by  hydrogenating  fish  or  whale  oil.  Miiller 
has  examined  this  product  *  and  has  reported  the  acid  number  as  12.8 
and  the  iodine  number  as  49.  The  fatty  acids  exhibited  a  titer  of 
39.4°  C.  When  Muller  attempted  to  saponify  the  fat  by  the  Twitchell 
process,  dark  colored  fatty  acids  were  produced,  caused,  it  is  supposed, 
by  oxidation  during  saponification.  Muller  observes  that  copper, 
iron  and  lead  tend  to  cause  a  discoloration  of  fat  which  is  treated  by 
the  Twitchell  process,  and  he  concludes  that  the  traces  of  nickel  which 
were  present  in  Talgit  acted  in  a  similar  manner.  When  he  subjected 
the  fat  to  cleavage  by  the  autoclave  process  very  light  colored  fatty 
acids  were  obtained.  A  pressure  of  10  to  11  atmospheres  was  main- 
tained in  the  autoclave  for  a  period  of  8  hours  and  the  resulting  fatty 
acids  were  found  to  contain  about  2.5  per  cent  of  unsaponified  fat. 
The  following  results  were  obtained  from  an  examination  of  the  fatty 
acids: 

Acid  number  of  the  fatty  acids 194 . 0 

Saponification  value  of  the  fatty  acids 198 . 0 

Titer 39.2°  C. 

Acid  number  of  the  liquid  fatty  acids 186 . 3 

Saponification  values  of  the  liquid  fatty  acids 191. 2 

Iodine  number  of  the  liquid  fatty  acids 100 . 0 

Titer  of  the  liquid  fatty  acids 14 . 3°  C. 

Titer  of  the  solid  fatty  acids 48 . 7°  C. 

The  fatty  products  of  the  saponification  pressed  very  readily  and 
about  35  per  cent  of  solid  fatty  acids  were  obtained  whose  low  titer 
(48.7°  C.)  indicates,  according  to  Muller,  that  fatty  acids  in  addition 
to  or  other  than  stearic  and  palmitic  acids  are  present,  for  the  solidify- 
ing point  of  mixtures  of  palmitic  and  stearic  acids  is  above  53.5°  C. 
The  presence  of  iso-oleic  acid  which  causes  a  lowering  of  the  titer  of 
stearic  acid  obtained  by  distillation  is  not  to  be  expected  in  this  case, 
but  Muller  has  not  further  investigated  the  acid  mixture  to  identify 
any  of  its  components.  As  the  fatty  acids  pressed  satisfactorily, 
Muller  concludes  that  the  stearic  acid  was  technically  pure,  hence  the 
low  titer  cannot  be  ascribed  to  the  presence  of  undue  amounts  of 
liquid  fatty  acids.  The  expressed  fatty  acids,  or  oleic  acid,  obtained 
as  stated  above,  exhibited  a  straw  yellow  color  and  showed  the  char- 
acteristic odor  of  hardened  fish  or  whale  oil.  Muller  states  that  for 
many  purposes  the  iodine  number  of  these  liquid  fatty  acids  is  too 
high.  He  concludes  that  so  far  as  this  product  is  concerned  the  hydro- 
genation  of  the  unsaturated  fatty  acids  does  not  proceed  successively 

*  Seifen.  Ztg.  (1913),  1376. 


USES  OF  HYDROGENATED  OILS  181 

so  as  to  convert  all  of  the  unsaturated  bodies  having  two  or  more 
double  bonds  into  bodies  having  only  one  double  bond  before  the 
latter  bodies  are  hydrogenated,  or  in  other  words  that  linoleic  and 
linolenic  acids  are  not  all  converted  into  oleic  acid  before  stearic 
acid  forms,  but  instead  of  this  that  reduction  takes  place  throughout, 
so  that  all  types  of  unsaturated  compounds  are  more  or  less  reduced 
simultaneously.  This  observation  is  of  interest  because,  as  Miiller 
notes,  the  presence  of  highly-unsaturated  bodies  of  the  nature  of  dry- 
ing oils  in  such  products  is  often  undesirable. 

Miiller  prepared  soap  from  Talgit  and  found  it  to  have  little  or  no 
detergent  and  lathering  properties  which  he  notes  is  to  be  expected 
with  fats  of  this  titer,  and  in  consequence  of  these  properties,  prod- 
ucts of  the  nature  of  Talgit  cannot  be  used  as  the  essential  fat  mate- 
rial, but  should  be  used  only  as  additions  to  the  main  fat  stock. 

Commenting  on  the  observation  of  Miiller  regarding  the  properties  of  Talgit, 
Dubovitz  (Seifen.  Ztg.  (1913),  1445)  notes  that  the  investigation  of  the  fatty  acids 
of  hardened  fish  oil  indicates  that  there  is  present  an  acid  whose  molecular  weight 
is  less  than  that  of  palmitic  acid.  Also  it  is  stated  that  it  is  possible  to  obtain  stearic 
acid  or  stearin  having  a  titer  of  53  to  55  degrees  from  strongly  hardened  fish  oil 
simply  by  pressing. 

Muller  (Seifen.  Ztg.  (1914),  8)  discusses  the  comments  of  Dubovitz  and  points 
out  that  mixtures  of  two  saturated  fatty  acids  crystallize  well  from  the  stearin 
manufacturer's  point  of  view,  while  mixtures  of  three  or  more  fatty  acids  as  a  rule 
produce  an  amorphous  mass. 

The  contention  of  Dubovitz  that  the  low  titer  of  stearin  can  be  explained  by 
the  presence  of  saturated  fatty  acids  with  less  than  16  carbon  atoms  in  the  molecule 
and  derived  from  the  corresponding  unsaturated  compounds  by  hydrogenation 
rests  on  the  assumption  of  the  existence  of  just  such  unsaturated  fatty  acids,  or 
their  glycerides,  in  fish  oils.  Proof  of  this  is  said  to  be  lacking  up  to  the  present. 
Even  the  presence  of  hypogeic  and  physetoleic  acids  in  these  oils  is  still  doubted. 
It  is  held  that  the  low  titer  of  the  stearin  in  question  was  due  to  the  presence  of 
unsaturated  fatty  acids.  (Seifen.  Ztg.  (1914),  33.) 

In  discussing  the  distillation  of  fatty  acids,  Hajek*  states  that 
some  difficulties  are  encountered  when  working  up  hydrogenated  oils 
to  produce  fatty  acids.  He  states  that  all  fats  which  are  treated  when 
hot  with  air  or  other  gases  for  a  considerable  length  of  time,  after  auto- 
clave saponification,  yield  dark  colored  fatty  acids  and  that  this  dis- 
coloration is  due  to  a  chemical  change  which  takes  place  in  coloring 
agents  present,  similar  in  character  to  that  which  occurs  in  the  distil- 
lation of  fatty  acids  at  elevated  temperatures,  or  with  an  insufficient 
proportion  of  superheated  steam. f 

*  Seifen.  Ztg.  (1913),  445. 

t  The  idea  which  has  been  entertained  that  hardened  triglycerides  could  be  directly 
used  for  candle  material  is  out  of  question,  as  no  one  would  care  to  inhale  the  vapors 


182  THE   HYDROGENATION  OF  OILS 

Norrnann  has  made  candles  with  stock  obtained  from  hardened  fish 
or  whale  oil  which  burned  brightly  and  without  odor,  similar  to  the 
best  grade  of  stearin  candles.* 

The  properties  of  hardened  castor  oil  have  been  noted  by  Garth. f 
As  is  generally  known,  castor  oil  differs  in  many  respects  from  other 
common  oils  in  such  respects  as  its  high  viscosity,  solubility  in  alcohol 
and  difficulty  of  salting  out  its  soaps  by  electrolytes.  The  constants 
of  one  sample  examined  by  Garth  are  as  follows : 

Acid  number 3.5 

Saponification  number 183 . 5 

Iodine  number 4.8 

Acetyl  number 153 . 5 

Acetyl  number  of  the  fatty  acids 143 . 1 

Acid  number  of  the  fatty  acids 184 .  5 

Saponification  number  of  the  fatty  acids 187 . 9 

Melting  point  of  the  fat 68°  C. 

Melting  point  of  the  fatty  acids 70°  C. 

Melting  point  of  the  acetylated  acids 47°  C. 

These  results  indicate  that  the  Saponification  and  acetyl  number 
do  not  change.  The  difference  between  the  acid  number  of  the  fatty 
acids  and  their  Saponification  number  points  to  the  formation  of 
lactones. 

From  the  point  of  view  of  soap  technics,  it  may  be  noted  that  the 
hardened  product  saponifies  with  dilute  lye  about  as  easily  as  common 

coming  from  candles  in  which  acrolein  was  being  generated.  Any  large  proportion 
of  nickel  in  the  fat  would  also  interfere  with  the  burning  qualities.  (Sach,  Zeitsch. 
f.  angew.  Chem.,  1913,  No.  94,  784.) 

The  slight  lathering  properties  of  soap  made  from  hardened  tran  is  to  be  expected, 
because  this  fat  finds  its  analogue  in  tallow.  Pure  tallow  soaps  are  very  difficultly- 
soluble  and  lather  very  poorly  so  the  same  property  may  be  looked  for  in  hardened 
fish  oil  or  whale  oil.  (Seifen.  Ztg.  (1912),  1003.) 

The  dark  colored  soaps  which  have  been  noted  by  some  users  of  hardened  oil 
may  be  due  to  traces  of  nickel  soap  in  the  oil  which  react  with  sulfur  compounds 
in  the  lye,  resulting  in  the  formation  of  nickel  sulfide  and  consequent  discoloration. 
(Seifen.  Ztg.  (1912),  1003.) 

The  odor  of  hardened  tran  is  very  much  like  that  of  distilled  oils  and  recalls 
the  penetrating  disagreeable  odor  which  is  observed  in  distillation  works  and  which 
is  apparently  due  to  the  partial  decomposition  of  fatty  acids  with  the  production 
of  acrolein  bodies.  Odors  of  this  character  materially  affect  the  quality  of  the  soap, 
but  this  trouble  may  be  avoided  if  greater  care  is  taken  in  the  hardening  process  to 
avoid  over-heating  of  the  oil  or  fat.  By  skillful  working  at  not  too  high  a  temper- 
ature, the  disagreeable  odor  does  not  appear  and  the  tran  is  rendered  completely 
odorless.  From  this  product  a  soap  may  be  made  which  is  beyond  criticism. 

*  Seifen.  Ztg.  (1914),  263. 

t  Seifen.  Ztg.  (1912),  1309. 


USES  OF  HYDROGENATED  OILS  183 

castor  oil.  Further,  soap  prepared  from  the  hardened  product,  in 
spite  of  its  high  melting  point,  like  castor  oil  soap,  has  a  similar  lack 
of  sensitiveness  against  salt  solutions  and  behaves  in  this  respect 
like  the  fats  of  the  cocoanut  oil  group.  Like  the  fats  of  the  latter 
group,  the  hardened  fat  may  be  saponified  at  a  temperature  of  about 
80°  to  90°  C.  While  a  soap  with  30  per  cent  fat  content  made  from 
ordinary  castor  oil  is  liquid,  the  corresponding  soap  from  hardened 
castor  oil  is  very  firm,  but  the  latter  soap  does  not  possess  the  prop- 
erty of  lathering  in  the  least. 

With  regard  to  tariff  rating  on  hardened  oil  Bohm  *  thinks  beyond 
question  the  hydrogenated  product  should  not  be  declared  and  rated 
like  the  untreated  oil  and  draws  an  analogy  between  raw  oils  and 
their  hydrogenated  products  and  formaldehyde  or  acetaldehyde  which 
yield  chemically  different  bodies,  respectively  methyl  and  ethyl  alcohol, 
by  taking  up  hydrogen. 

It  is  contended  f  that  Bohm's  illustrative  use  of  formaldehyde, 
which  body  through  the  addition  of  two  atoms  of  hydrogen  is  trans- 
formed into  methyl  alcohol  and  thus  into  an  essentially  different 
body  from  the  tariff  point  of  view,  is  not  entirely  analogous  with 
respect  to  hardened  oils,  for  oils  are  not  unitary  chemical  individuals, 
but  are  mixtures  of  triglycerides  of  various  fatty  acids.  Also  it  is 
held  that  hydrogenated  oils  are  not  essentially  single  chemical  individ- 
uals like  tristearin,  but  are  mixtures  of  various  fatty  acid  triglycerides 
in  which  mixtures,  of  course,  tristearin  is  present  in  much  greater 
quantities  than  in  the  original  oil.  A  differentiation  for  tariff  pur- 
poses on  the  ground  of  chemical  composition  is  thus  practically  im- 
possible.:]: 

Dr.  Bela  Lach,  in  the  Seifen.  Ztg.  (1912),  1245,  discusses  American  soap  manu- 
facture and  refers  to  the  Fels  Naptha  Soap  Works  of  Philadelphia,  as  being  users 
of  hydrogenated  oil.  He  says  that  Fels  Naptha  soap  contains  from  10  to  15  per  cent 
of  benzene  of  high  boiling  point,  and  that  the  raw  materials  are  in  a  large  part  cotton 
and  corn  oil.  Only  a  relatively  small  proportion  of  hard  stock,  such  as  tallow  or 

*  Seifen.  Ztg.  (1912),  738. 

t  Seifen.  Ztg.  (1912),  1003. 

t  An  article  by  Harmsen  (Seifen.  Ztg.  (1913),  638-39  and  661-62)  discusses  the 
matter  of  tariff  adjustment  of  hardened  fats,  and  he  states  that  by  the  hardening 
operation  the  consistency  and  other  qualities  of  the  oil  are  so  modified  that  a  recog- 
nition of  its  origin  is  in  most  cases  impossible  either  by  taste,  smell  or  chemical 
test.  Chemical  analysis  can  determine  only  whether  the  fat  is  of  animal  or  vegetable 
origin.  The  Hamburg  authorities  have  arrived  at  the  conclusion  that  hardened 
fat  or  oil  must  be  taxed  according  to  the  properties  and  quality  acquired  by  harden- 
ing. Harmsen  also  discusses  the  position  of  Talgol  from  the  tariff  standpoint  in 
Seifensieder  Zeitung  (1913),  745. 


184  THE  HYDROGENATION  OF  OILS 

palm  kernel  oil,  is  used.  The  amount  of  this  material  employed  is,  however,  reduced 
because  this  concern  has  been  able  to  make  use  of  hydrogenated  oil,  a  material 
which  they  have  thoroughly  tested.  At  this  plant  Lach  states  he  saw  samples  of 
hardened  cotton  and  corn  oil,  as  well  as  various  kinds  of  hardened  fish  oil  which 
were  of  a  remarkably  fine  character.  They  had  the  hardness  and  appearance  of 
fine  tallow,  were  beyond  criticism  as  to  odor  and  could  be  worked  up  into  a  soap  in 
a  satisfactory  manner. 

A  hardened  oil  of  relatively  low  titer,  bearing  the  trade  name  of  "Krutolin"  (or 
Crutolin),*  is  discussed  in  the  Seifensieder  Zeitung  (1913),  930  and  954,  and  as  some 
of  the  observations  may  be  of  use  in  the  handling  of  other  more  or  less  similar  hydro- 
genated products  the  following  data  is  here  included. 

On  account  of  the  great  demand  for  good  fats  and  oils  in  edible-fat  manufacture, 
the  prices  of  these  have  increased  very  materially,  and  it  has  become  continually 
more  difficult  to  obtain  fats  which  remain  white  on  boiling.  Therefore  hardened 
oils  such  as  Krutolin,  which  may  be  obtained  of  uniformly  good  quality,  promise 
to  be  of  decided  utility.  It  is  said  that  Krutolin  has  the  advantage  of  being  cheaper 
than  lard  and  cottonseed  oil,  and  that  in  addition  it  is,  as  has  been  proven  by  long- 
continued  experiments,  a  good  substitute  for  lard  and  white  cottonseed  oil.  When 
used  for  barrel  soaps,  Krutolin,  alone,  has  a  tendency  to  form  sirupy,  stringy  soaps. 
Therefore,  it  is  desirable  to  supplement  it  by  the  proper  addition  of  other  fats.  In 
practice  it  has  been  shown  that  the  danger  of  " lengthening"  of  unfilled  white  soft 
soaps  is  greater  than  when  more  or  less  potato  flour  is  used  as  a  filler.  Hence  it  is 
recommended  that  the  percentage  of  Krutolin  employed  be  kept  somewhat  lower 
for  such  unfilled  products. 

As  mutton  tallow,  cottonseed  oil,  peanut  oil  and  lard,  or  their  fatty  acids,  in  Ger- 
many are  the  usual  or  principal  raw  materials  for  white  soft  soap,  it  is  stated  that 
under  present  market  conditions  a  considerable  saving  is  attained  in  the  manufac- 
ture of  soaps  if  these  fats  are  replaced,  even  only  in  part,  by  Krutolin.  In  combi- 
nation with  the  above-named  raw  materials  Krutolin  furnishes  a  very  white  soap  for 
both  unfilled  or  filled  goods.  It  is  self-evident  that  a  primary  condition  for  the 
production  of  a  totally  white  soap  is  cleanliness  of  working.  Furthermore,  it  is 
necessary  to  pay  attention  to  the  alkali  and  especially  the  potato  flour  as  these  are 
often  of  varying  origin,  and  are  not  always  suitable.  Many  50-degree  caustic 
potash  lyes  give  perfectly  water-white  solutions  when  diluted;  others,  however,  show 
a  yellow  tone.  With  filled  soaps  the  quality  of  the  potato  flour  has  a  strong  influ- 
ence on  the  character  of  the  finished  product.  Every  shipment  should  be  tested 
for  color  and  to  ascertain  whether  the  flour  has  been  treated  with  acid.  Potato 
flours  containing  acid  are  to  be  excluded  for  filling  white  soft  soaps,  as  they  produce 
an  after-darkening.  The  kind  of  water  used  also  has  some  influence  on  the  color 
of  these  soaps. 

A  stock  for  unfilled  figged  soap  containing  Krutolin  follows: 

1500  kg.  mutton  tallow 

900  kg.  cottonseed  oil 

600  kg.  Krutolin 
3000  kg. 

On  account  of  the  high  titer  which  mutton  tallow  possesses  and  in  recognition 
of  the  fact  that  Krutolin  easily  favors. the  "lengthening"  of  the  soap,  one  must 

*  Krutolin  is  stated  to  be  a  substitute  for  "technical"  lard  and  American  cotton 
oil  (Seifen.  Ztg.  (1913),  1386). 


USES  OF  HYDROGENATED  OILS   .  185 

from  the  beginning  count  on  a  strong  increase  of  carbonated  alkali  to  reduce  the 
causticity  of  the  caustic  potash  lye.  It  is  possible,  in  the  above  stock,  to  use  30  kg. 
96  to  98  per  cent  potash  to  100  kg.  of  50-degree  caustic  potash  lye.  It  will  often 
be  advisable,  especially  during  the  warm  season,  to  substitute  ammonia  soda  solu- 
tion for  a  part  of  the  potash  solution,  in  order  to  secure  an  easy  and  rapid  figging  of 
the  soap. 

After  completion  of  the  boiling,  samples  are  to  be  carefully  tested  to  ascertain 
if  the  soap  has  been  sufficiently  shortened  by  carbonated  alkali.  Samples  placed 
on  glass  must  remain  liquid  a  long  time,  and  on  stirring  after  cooling  must  not  show 
any  stringiness.  Should  the  soap  still  remain  tough  and  gum-like  a  later  addition 
of  concentrated  potash  or  soda  solution  is  necessary  in  order  to  produce  a  satisfac- 
tory product.  On  account  of  the  large  amount  of  carbonated  alkali  which  can  be 
absorbed,  the  yield  of  this  soap  is  very  good. 

The  mutton  tallow  can  be  omitted  and  a  somewhat  larger  amount  of  white  lard 
substituted.  The  composition  would  then  be  about  as  follows: 

1600  kg.  lard 
750  kg.  cottonseed  oil 
650  kg.  Krutolin 
3000kg. 

As  lard  has  a  considerably  lower  titer  than  mutton  tallow,  the  amount  of  shorten- 
ing material  used  with  this  stock  must  be  decreased  accordingly.     With  the  stock 
first  given,  which  contained  a  large  amount  of  mutton  tallow,  additions  of  caustic 
soda  lye  were  not  necessary,  but  in  this  case,  where  softer  fats  form  the  basis,  it  is 
advisable  to  add  about  20  per  cent  of  caustic  soda  lye  in  the  boiling.     The  neutral 
fats  in  this  stock  can  be  replaced  by  fatty  acids,  but  as  soaps  from  neutral  fats  are 
whiter,  this  is  not  to  be  recommended.     A  moderate  filling  with  flour  is  advanta- 
geous when  using  fatty  acid  stock.     A  figged  soap  with  a  little  filling  can  hardly  be 
distinguished  by  visual  examination  from  one  which  is  unfilled.     For  the  above 
stock  of  3000  kg.  the  following  filler  is  recommended: 
300  kg.  best  potato  flour. 
600  kg.  12-degree  potash  solution. 
300  kg.  lye,  30°  B<§, 

The  filler  is  to  be  added  in  the  morning  if  the  soap  has  cooled  sufficiently  over  night. 
The  soap  is  perfumed  with  sal-ammoniac,  turpentine,  safrol,  oil  of  camphor,  lemon 
oil  or  suitable  mixtures  of  these. 

For  a  first-class  "sal-ammoniac-turpentine"  soft  soap,  where  particular  value  is 
laid  upon  the  resulting  white  color,  and  less  on  the  figged  effect,  mutton  tallow  and 
cottonseed  oil  may  be  left  out  and  Candelite  and  Talgol  substituted  in  part  therefor. 
The  composition  would  then  be  the  following: 

2000  kg.  Krutolin. 
1000  kg.  Candelite. 

For  the  reduction  of  the  causticity  30  kg.  potash  should  be  used  to  every  100  kg. 
50-degree  caustic  potash  lye.  On  boiling  about  one-third  caustic  soda  is  to  be  added. 
To  the  latter  25  kg.  ammonia  soda  are  added  to  every  100  kg.  soda.  These  alkalies 
are  dissolved  separately,  mixed  and  the  lye  diluted  to  the.  required  strength. 

The  above  stock  gives  a  soap  of  special  toughness.  Therefore,  it  may  be  neces- 
sary to  add  more  or  less  soda  or  potash  solution  according  to  the  result  of  tests  made 
from  time  to  time,  until  the  soap  possesses  the  desired  normal  characteristics.  "Sal- 
ammoniac  turpentine  soap"  made  according  to  this  formula  possesses  a  very  white 


186  THE  HYDROGENATION  OF  OILS 

color  and  by  use  of  first-class  potato  flour  can  be  filled  up  to  25  per  cent  without 
influencing  the  color. 

The  filler  is  made  up  as  previously  mentioned,  but  must  have  an  addition  of 
potash  filler.  Its  make-up  thus  becomes: 

750  kg.  potato  flour. 
1500  kg.  12-degree  potash  solution. 
375  kg.  potash  filler. 
750  kg.  30-degree  "  take-off  "  lye. 

In  order  to  more  surely  prevent  the  lengthening  of  the  soap  ammonia-soda  solu- 
tion also  may  be  used  in  part  in  the  filler  instead  of  potash  solution.  For  second 
and  third  quality  soap  which  can  be  filled  in  a  similar  manner  with  50  and  75  per 
cent  of  potato  flour,  the  formula  and  boiling  remain  the  same.  These  filled  "sal- 
ammoniac  turpentine"  soaps  should  be  perfumed  rather  strongly  with  sal-ammoniac 
and  some  turpentine,  for  prospective  purchasers  judge  the  soap  not  only  by  its 
white  color,  but  also  by  the  more  or  less  strong  ammoniacal  odor. 

As  already  mentioned,  the  yield  of  such  soaps  is  said  to  be  increased  by  the  use 
of  Krutolin.  This  is  explained  by  the  increased  ability  to  take  shorten ers.  For 
example,  a  "sal-ammoniac  turpentine"  soap  filled  with  50  per  cent  potato  flour, 
gave  a  yield  of  about  250  per  cent. 

Krutolin  is  not  available  for  natural  grain  and  green  soft  soaps,  as  here  its  qual- 
ities do  not  make  it  a  substitute  for  either  tallow  or  linseed  oil.  Tallow  is  necessary 
for  natural  grain  soaps;  at  least  up  to  now  it  has  been  impossible  to  produce  a 
faultless  grain  formation  with  Krutolin  or  Talgol.  Krutolin  is  also  not  suited  for 
a  perfectly  clear  transparent  soft  soap. 

From  long  continued  tests  in  a  large  way  it  has  been  shown  that  Krutolin  can 
also  be  added  to  the  stock  used  in  making  bar  soaps,  insuring  light  color  with  good 
pressing  qualities. 

A  stock  giving  a  light  yellow  soap  which  presses  well,  is  the  following : 
1200  kg.  Krutolin 
1200  kg.  fatty  acids  of  Talgol 
300  kg.  fatty  acids  of  by-product  cocoanut  oil 
300  kg.  fatty  acids  of  palm  kernel  oil 
3000kg. 

450  kg.  rosin  =  15  per  cent 
3450kg. 

Under  normal  treatment  and  good  cooling  the  above  stock  will  furnish  a  soap  of 
adequate  firmness.  Of  course,  the  amount  of  rosin  added  has  an  important  influ- 
ence on  the  solidity  of  the  soap.  With  large  amounts  of  rosin  the  use  of  soft  fats 
must  be  minimized,  as  otherwise  there  is  danger  of  obtaining  too  soft  a  soap  in  spite 
of  the  cooling  treatment. 

A  stock  with  20  per  cent  rosin  has  the  following  composition: 
800  kg.  Krutolin 

600  kg.  fatty  acids  of  light  bone  fat 
1000  kg.  fatty  acids  of  Talgol 
300  kg.  fatty  acids  of  by-product  cocoanut  oil 
300  kg.  fatty  acids  of  palm  kernel  oil 
3000kg. 

600  kg.  rosin  =  20  per  cent 
3600kg. 


USES  OF  HYDROGENATED  OILS  187 

To  obtain  sufficiently  solid  soaps  it  is  important  to  separate  sharply  on  salting  out 
so  as  to  secure  a  good  grain.  By  doing  this  the  appearance  of  cake  soap  may  be 
somewhat  marred.  This,  it  is  further  stated,  is  not  to  be  feared  so  much  with  cooled 
soaps,  as  undesirable  segregation  cannot  occur  to  any  material  extent  during  the 
rapid  solidification.  This  is  one  of  the  main  advantages  of  cooling  machines  in 
addition  to  the  rapid  production  of  goods  ready  for  shipment.  If  only  by-product 
cocoanut  or  palm  kernel  oil  from  edible  fat  manufacture  are  to  be  used  for  the  stock 
instead  of  the  best  palm  kernel  fatty  acid,  it  will  be  necessary  to  reduce  the  propor- 
tion of  rosin  as  the  resulting  soap  may  otherwise  be  too  soft.  These  by-product 
cocoanut  or  palm  nut  oils  almost  always  contain  sesame  or  other  similar  oils,  and 
influence  the  soap  produced  from  them.  When  Krutolin  is  used  in  this  manner  it 
is  advisable  to  perfume  with  safrol,  lemon  oil,  etc.,  before  cooling  in  order  to  cover 
the  peculiar  odor  of  this  raw  material  which  is  disagreeable  to  some  people. 

For  settled  yellow  rosin  grain  soaps  Krutolin  can  also  be  used  to  advantage  as 
it  improves  the  base  for  later  coloring.  The  action  of  crude  palm  oil  used  for  color- 
ing will  be  materially  stronger  with  a  clear  soap  base,  than  if,  for  instance,  dark 
bone  fat  has  produced  a  base  difficult  to  cover. 

The  composition  of  the  stock  is  the  following: 

600  kg.  by-product  cocoanut  oil 

900  kg.  Krutolin 

600  kg.  fatty  acids  of  light  bone  fat 

450  kg.  fatty  acids  of  Talgol 

450  kg.  crude  palm  oil 
3000kg. 

600  kg.  rosin  =  20  per  cent 
3600kg. 

Here  also  the  condition  of  the  finished  soap  must  be  the  regulator  for  its  com- 
position. For  instance,  if  the  soap  is  too  soft,  the  percentage  or  rosin  or  Krutolin 
is  to  be  reduced. 

Krutolin  also  finds  a  use  in  making  white  wax  grain  soaps  and  various  grades  of 
textile  soaps.  Where  the  kind  and  color  of  the  soaps  allow,  as  has  been  repeatedly 
found  with  textile  soaps,  Krutolin  should  be  split,  in  order  not  to  lose  the  glycerine. 

Krutolin  can  be  used  to  advantage  as  an  addition  fat  in  making 
soaps  by  the  cold  process,  although  care  should  be  taken  in  its  use. 
With  unfilled  toilet  soaps  about  30  per  cent  Krutolin  may  be  used 
with  about  70  per  cent  of  cocoanut  oil.  If  the  soap  is  to  be  filled, 
the  percentage  of  Krutolin  should  be  correspondingly  reduced,  since 
otherwise  the  soap  would  suffer  in  appearance  and  would  be  poorly 
bonded.* 

In  preparing  a  white  soft  soap  Bergo  (Seifen.  Ztg.  (1913),  1220)  uses  1000  kg. 
fatty  acids  of  cotton  oil  to  200  kg.  of  Candelite.  900  kg.  of  30°  Be",  caustic  potash 
lye  and  300  kg.  of  25°  Be",  caustic  soda  lye  are  used  together  with  100  kg.  of  car- 
bonate of  soda  lye  of  30°  Be".  The  caustic  potash  lye  is  reduced  with  carbonate  of 

*  Seifen.  Ztg.  (1914),  8. 


188  THE  HYDROGENATION  OF  OILS 

potash  solution.     The  lyes  are  put  in  the  kettle  first,  the  fatty  acids  slowly  added 
and  then  the  Candelite.*     (Chem.  Abs.  (1914),  588.) 

Hydrogenated  linseed  oil  has  been  put  on  the  market  under  the 
name  of  "  Linolith "  by  the  Germania  Olwerke.f  Two  grades  are 
manufactured.  One  grade  has  a  melting  point  of  45°  C.,  and  the 
other  melts  at  55°  C.  Both  grades  show  a  saponification  number 
of  188  to  195  and  a  glycerine  content  of  9  to  10  per  cent.  Linolith 
has  not  been  used  extensively  in  white  soaps  as  it  is  off  color,  but  is 
serviceable  for  the  preparation  of  rosin  or  "Eschweger"  soaps  and  the 
like.  While  the  raw  material,  linseed  oil,  is  liable  to  cause  yellowing 
or  after-darkening  of  soaps  or  the  sweating  out  of  drops  of  a  yellow 
liquid,  the  hardened  oil  is  thought  to  be  free  from  these  objections, 
but  caution  is  advised  in  its  use  until  thorough  tests  have  been  carried 
out.J 

Soaps  made  with  hardened  linseed  oil  (Linolith)  and  rosin  are  of  good 
quality  and  the  odor  and  color  are  excellent.!  The  following  formulae 
have  been  tested: 

*  The  character  of  soaps  made  from  hardened  oil  in  conjunction  with  cottonseed 
or  peanut  oil  is  discussed  in  Der  Seifenfabrikant  (1913),  31. 

t  Talgol,  Candelite,  Krutolin  and  Linolith  have  taken  a  place  in  the  German 
market  and  are  listed  among  the  fats  regularly  quoted.  (See  Seifen.  Ztg.  (1913), 
1386.) 

In  Germany  the  price  of  fish  and  whale  oils  fluctuates  to  some  extent  with  that  of 
linseed  oil  by  reason  of  the  demand  for  these  oils  by  oil-hardening  concerns.  (Seifen. 
Ztg.  (1913),  1385.) 

Linseed  oil  is  in  increased  demand  for  the  manufacture  of  hardened  oils  and  edible 
compounds.  It  is  stated  that  in  North  America  this  oil  promises  to  become  an  im- 
portant raw  material  for  the  hydrogenation  industry.  (Seifen.  Ztg.  (1913),  1277.) 

R.  H.  Adams,  president  of  the  American  Linseed  Company,  attributes  consider- 
able importance  to  the  hardening  process  as  applied  to  linseed  oil.  "The  hydro- 
genation process,"  Adams  states,  "is  merely  in  its  infancy  and  is  bound  to  exert  a 
powerful  influence  upon  the  oil  markets,  and  will  prevent  the  price  of  linseed  oil  from 
ever  going  to  the  low  levels  which  have  been  reached  in  certain  years  of  the  past." 
He  states  that  the  process  would  not  affect  linseed  oil  alone,  but  as  the  process  was 
applicable  to  other  vegetable  oils  and  to  fish  oils,  the  question  of  comparative  prices 
would  largely  determine  the  extent  of  consumption  in  the  case  of  each  oil.  The 
increased  outlet  for  linseed  oil  afforded  by  virtue  of  the  hydrogenation  process  was 
generally  credited  to  the  soap  trade.  While  consumption  of  oil  for  soap-making  pur- 
poses undoubtedly  has  increased,  Adams  states  that  another  outlet,  and  one  which 
may  assume  very  large  proportions,  is  found  in  the  edible  trades,  and  even  now  large 
quantities  of  linseed  oil  are  being  thus  consumed  on  the  Continent.  (O.  P.  &  D.  R., 
March  10,  1914.) 

t  Seifen.  Ztg.  (1913),  1299. 

§  Seifen.  Ztg.  (1914),  231. 


USES  OF  HYDROGENATED  OILS 


189 


A 

B 

C 

D 

Linolith  M   P.  45°  C.,  or  its  fatty  acids.  . 

1600  Ibs. 

1600  Ibs. 

Linolith  extra,  M.  P.  55°  C.,  or  its  fatty 
acids                                

1500  Ibs 

1500  Ibs 

Fatty  acids  of  palm  kernel  oil  .  .             ... 

400 

200 

400 

300 

Fatty  acids  of  cocoanut  oil           .      

200 

Fatty  acids  of  peanut  oil  

300 

500 

500 

Fatty  acids  of  Talgol  

500 

300 

Soft  fat                          

500 

700 

300 

700 

Rosin               .         

750 

1050 

900 

1200 

The  fatty  acids  were  saponified  with  carbonate  and  the  neutral  fat 
with  30  degree  caustic  soda.  The  Linolith  extra  was  found  capable  of 
carrying  a  higher  proportion  of  rosin  than  the  regular  Linolith. 

Linolith  does  not  exhibit  any  marked  odor  such  as  is  observed  in 
the  case  of  much  of  the  hardened  fish  oil  on  the  market  and  is  regarded 
as  suitable  for  the  manufacture  of  white  grained  soaps.*  The  follow- 
ing procedure  has  been  tried  and  a  satisfactory  product  obtained. 
50  parts  of  Linolith,  10  parts  of  a  tallowy  fat  and  40  parts  of  fatty 
acids  derived  from  a  vegetable  oil  were  employed.  The  Linolith  and 
tallowy  fat  were  saponified  and  it  was  noted  that  saponification  pro- 
gressed rapidly.  The  product  was  bleached  with  Blankit  and  salted 
out.  After  settling  it  was  combined  with  stock  derived  from  the 
separate  saponification  of  the  vegetable  oil,  and  well  boiled  and  salted 
out.  The  soap  was  duly  grained  and  afforded  a  product  of  excellent 
feel  and  good  odor.  The  color  was  not  a  pure  white. 

The  difficulties  in  using  hydrogenated  linseed  oil  (Linolith)  in  white- 
grained  soaps,  according  to  Wilhelmus,f  have  been  that  the  color  was 
not  sufficiently  light  and  the  lathering  properties  were  deficient.  The 
texture  of  the  soap  was  unsatisfactory  and  cracks  occurred  on  standing. 
In  investigations  directed  toward  the  elimination  of  these  objectionable 
features  Wilhelmus  found  that  much  depended  on  the  manner  of  cleav- 
age of  the  hardened  linseed  oil.  While  with  autoclave  treatment 
saponification  to  the  extent  of  88  to  90  per  cent  gave  fatty  acids  of  good 
color,  it  was  not  found  feasible  with  the  Twitchell  reagent  to  exceed 
80  to  82  per  cent,  as  the  resulting  fatty  acids  otherwise  were  too  dark 
for  white  soaps.  Pfeilring  reagent  afforded  better  results  and  Wilhel- 
mus regards  this  cleavage  compound  to  be  of  specific  value  in  splitting 
hardened  oils.  Benefit  is  derived  by  adding  to  hydrogenated  linseed 
oil  a  quantity  of  an  oil,  such  as  peanut  oil,  which  splits  easily,  yielding 
light  colored  fatty  acids.  By  subjecting  the  hardened  oil  to  cleavage 
under  these  conditions  a  better  grade  of  fatty  acid  may  be  obtained. 
*  Seifen.  Ztg.  (1914),  140  and  167. 
t  Seifen.  Ztg.  (1914),  257. 


190  THE  HYDROGENATION  OF  OILS 

In  making  the  soap  about  40  per  cent  of  hydrogenated  linseed  oil 
(Linolith)  may  be  employed.  After  saponification  with  alkali  and 
graining  in  the  kettle,  the  product  is  bleached.  For  this  purpose  a 
bleach  consisting  of  91  parts  of  water,  5.8  parts  of  sodium  bisulfite,  2 
parts  of  sulfuric  acid  and  1.35  parts  of  zinc  dust  are  used  for  1000  parts 
by  weight  of  the  fat.  The  use  of  soap-cooling  apparatus,  in  place  of 
frames,  enables  a  better  control  of  the  color.  The  addition  of  10  to 
15  per  cent  of  castor  oil  improves  the  solubility  and  lathering  qualities  of 
the  soap.  15  per  cent  of  castor  oil  is  the  maximum.*  If  still  higher 
lathering  properties  are  required  "Saponin"  powder  may  be  added. 

*  The  preparation  of  soaps  with  fatty  mixtures  consisting  of  saturated  fats,  such 
as  those  derived  by  hydrogenation,  with  unsaturated  fats  or  oils  has  been  made  the 
basis  of  an  application  for  German  Patent  by  Worms  and  the  novelty  of  the  idea  is 
criticized  in  Seifensieder  Zeitung,  1914,  392. 


CHAPTER  XI 
HYDROGENATION   PRACTICE 

Whether  or  not  the  plant  is  to  treat  animal  or  vegetable  oils,  or 
fish  oil,  the  following  general  procedure  may  be  laid  down  for  guidance 
in  the  equipment  and  operation  of  a  hydrogenating  works. 

The  starting  point  is,  perhaps,  the  preparation  of  catalyzer.  Of 
course  the  procedure  employed  for  its  preparation  depends  on  the 
type  of  catalyzer  selected.  Suppose  nickel  be  chosen  as  the  active 
material,  to  be  used  on  a  suitable  carrier  or  supporting  base.  To  this 
end  a  solution  of  a  nickel  salt,  such  as  the  nitrate  or  sulfate,  is  mixed 
in  vats  with  the  support,  in  the  presence  of  a  precipitant,  or  the 
latter  is  subsequently  added,  and  the  material  is  well  agitated.  Solu- 
ble salts  should  then  be  removed  by  washing  and  the  material  dried. 
These  operations  may  take  place  in  a  filter  press  supplied  with  air 
under  pressure.  The  caked  product  should  be  ground  in  a  ball  or 
pebble  mill  until  resolved  into  a  fine  powder. 

The  catalyzer  is  now  ready  for  reduction,  which  should  be  per- 
formed with  extreme  care  as  the  entire  oiUhardening  process  depends 
on  the  efficiency 'of  the  catalyzer.  A  -simple  and  efficient  type  of 
catalyzer-reducing  device  is  represented  by  Fig.  55.  A  is  a  brick 
structure  which  contains  the  reducing  drum  B.  The  latter  is  rotated 
by  means  of  the  sprocket  C.  E1E2  are  stuffing  boxes  which  admit 
of  rotating  the  drum  without  disturbing  the  gas  inlet  and  outlet. 
The  catalyzer  is  admitted  and  withdrawn  through  the  gate  G.  The 
drum  is  filled  about  two-fifths  full  of  the  catalyzer  and  hydrogen 
passed  in.  When  tests  for  oxygen  show  that  all  the  air  has  been 
expelled  the  drum  is  heated  to  a  temperature  not  exceeding  360°  C. 
During  reduction  the  hydrogen  is  passed  through  at  a  considerable 
rate  in  order  to  remove  the  steam  formed,  thus  reducing  the  partial 
pressure  of  the  latter  and  facilitating  the  reduction  of  the  nickel 
oxide  or  hydrate.  The  gases  issuing  from  the  exit  side  of  the  drum 
may  pass  through  a  water  seal  and  after  purification  may  be  returned 
to  the  gas  holders  to  be  used  again.  When  the  issuing  gases  are  found 
to  contain  no  steam  the  reduction  is  complete,  the  heating  is  dis- 
continued and  the  catalyzer  allowed  to  cool  in  a  current  of  hydrogen. 

191 


192 


THE  HYDROGENATION   OF  OILS 


After  cooling  the  catalyzer,  the  hopper  shown  in  Fig.  55  is  coupled 
to  the  flange  of  the  gate  G.  The  bottom  of  the  hopper  dips  below  the 
surface  of  oil  contained  in  a  receptacle  beneath.  Hydrogen  is  passed 
in  at  the  valve  J  and  the  air  is  thereby  expelled  from  the  hopper. 
The  valve  of  the  reducing  drum  is  now  opened  and  the  catalyzer 
allowed  to  fall  into  the  oil  with  which  it  should  be  thoroughly  mixed. 
Thus  the  catalyzer  is  effectively  sealed  from  the  air. 


FIG.  55. 


This  method  of  abstracting  catalyzer  from  the  reducing  drum  pre- 
vents oxidation  of  the  nickel  which  occurs  to  a  greater  or  less  extent 
when  the  catalyzer  is  withdrawn  in  contact  with  the  air. 

The  catalyzer  in  oil  may  then  be  transferred  to  a  large  agitating 
tank  in  which  oil  is  added  in  sufficient  quantity  to  make  the  mixture 
contain  the  correct  percentage  of  catalyzer.  The  contents  are  thor- 
oughly agitated  and  transferred  to  the  hydrogenator  where  the  actual 
hydrogenation  takes  place. 

Tall  iron  tanks  may  be  used  for  this  purpose,  one  type  of  which  is 
shown  in  Fig.  56.  The  air  in  the  hydrogenator  is  displaced  by  means 
of  hydrogen  and  the  mixture  of  catalyzer  and  oil  pumped  from  the 


HYDROGENATION  PRACTICE 


193 


agitator  A  into  the  hydrogenator  C.  The  contents  of  the  hydro- 
genator  are  heated  to  a  temperature  of  175°  to  190°  C.  by  means  of 
superheated  steam  or  hot  oil  coils,  the  latter  being  preferable  owing 
to  the  danger  of  leakages  of  steam  into  the  chamber.  The  tempera- 
ture of  the  contents  of  the  hydrogenator  should  be  registered  by 
means  of  a  reliable  thermometer,  preferably  a  recording  pyrometer. 


FIG.  56. 

The  oil  and  catalyzer  in  the  hydrogenator  are  circulated  by  means 
of  the  rotary  pump  E,  which  takes  the  liquid  from  the  bottom  of  the 
hydrogenator  and  pumps  it  through  the  inductor  /  where  hydrogen 
drawn  from  the  gas  space  at  the  top  of  the  hydrogenator  is  mixed  with 
the  oil.  CK  is  a  check  valve  to  prevent  oil  from  entering  the  tank 
through  the  suction  tube  in  the  event  of  the  inductor  suction  nozzle 
becoming  flooded.  The  mixture  of  oil,  catalyzer  and  hydrogen  is 
ejected  through  the  distributor  D  at  the  bottom  of  the  hydro- 
genator. 

The  hydrogen  inlet  is  provided  with  a  safety  device  M  and  a 
pressure  gauge  P3. 


194  THE  HYDROGENATION  OF  OILS 

The  pressure  maintained  in  the  hydrogenator  is  variable  according 
to  the  oil  under  treatment  and  may  range  from  atmospheric  or  less 
up  to  about  25  pounds.*  The  difference  in  the  readings  of  the  pres- 
sure gauges  PiPz  registers  the  suction  of  hydrogen  at  the  suction  nozzle 
of  the  inductor.  Samples  of  oil  may  be  withdrawn  from  time  to  time 
from  the  outlet  Q.  When  the  sample  indicates  that  the  oil  has  the 
required  hardness  the  hydrogenator  is  emptied  through  the  outlet  V 
and  the  contents  are  run  into  large  tanks  which  are  heated  by  means 
of  steam  coils.  From  these  tanks  the  mixture  of  oil  and  catalyzer  is 
pumped  into  filter  presses  where  the  catalyzer  is  removed.  The  oil 
is  finally  run  into  cooling  tanks  where  it  solidifies  to  a  hard  fat  ready 
to  be  made  into  lard  compound,  soap  or  other  product. 

The  transformation  to  olein  of  the  glycerides  of  linoleic  and  linolenic 
acids  or  other  highly  unsaturated  acids  usually  does  not  result  in  any 
marked  change  in  the  titer.  As  these  bodies  sometimes  are,  to  a  con- 
siderable extent,  transformed  into  olein  before  olein  becomes  stearin, 
hydrogen  will  be  absorbed  by  the  oil  without  hardening,  to  a  degree 
dependant  on  the  proportion  of  these  highly  unsaturated  bodies 
present.  Often  an  hour  or  more  is  needed  to  bring  an  oil  to  the 
"  olein  stage,"  after  which  hardening  will  progress  rapidly. 

Of  course,  the  method  given  above  is  capable  of  many  modifications, 
as  oils  of  different  character  require  different  treatment  and  in  con- 
sequence oftentimes  call  for  equipment  which  varies  considerably 
from  that  given  by  way  of  illustration.  Catalyzers  vary  a  good  deal 
in  their  properties,  and  conditions  which  are  suitable  for  nickel  in 
some  of  its  forms  will  not  answer  for  palladium.  A  much  lower 
temperature  usually  suffices  when  using  the  latter  metal  as  a  catalytic 
substance. f 

*  One  of  the  difficulties  met  with  in  the  handling  of  hydrogen  has  been  the  loss 
by  leakage  of  the  gas.  Under  pressure  and  at  a  temperature  of  150°  or  200°  C., 
hydrogen  is  surprisingly  penetrating.  Autoclaves  with  welded  seams  are  desirable 
for  high-pressure  and  high-temperature  work.  Moving  parts  should  be  avoided  as 
far  as  possible. 

t  Reference  is  made  to  the  chapter  on  catalyzers  which  gives  much  detailed 
information  on  the  subject.  Attention  is,  however,  called  to  the  existence  of  several 
patents  covering  certain  forms  of  catalytic  preparations. 


CHAPTER  XII 
THE   HYDROGEN   PROBLEM   IN   OIL  HARDENING 

Oleic  acid  and  hydrogen  combine,  molecule  for  molecule,  to  yield 
stearic  acid  according  to  the  reaction: 


Thus  282  pounds  of  oleic  acid  require  2  pounds  (or  about  0.7  per 
cent)  of  hydrogen  for  the  production  of  284  pounds  of  stearic  acid, 
and  similarly  the  transformation  of  olein  into  stearin  requires  the 
use  of  about  0.68  per  cent  hydrogen.* 

One  thousand  cubic  feet  of  hydrogen  weigh  approximately  5.6 
pounds,  hence  a  pound  of  olein  calls  for  a  little  over  0.1  of  an  ounce 
of  hydrogen  equivalent  to  approximately  2500  cubic  feet  of  hydrogen 
per  ton  (of  2000  pounds)  of  olein.  Thus  by  weight  only  a  relatively 
small  quantity  of  hydrogen  is  needed,  while  by  volume  the  amount 
required,  of  course,  is  considerable.  f 

*  The  amount  of  hydrogen  required  for  complete  conversion  is  given  by  Sachs 
(Zeitsch.  f.  angew.  Chem.,  1913,  94,  784)  as  7.4  kilos  or  85  cubic  meters  hydrogen 
per  1000  kilos  oleic  acid.  1000  kilos  of  linoleic  acid  having  two  double  bonds  call 
for  14.2  kilos,  or  170  cubic  meters  of  hydrogen.  1000  kilos  of  linoleic  with  three 
double  bonds  need  21.6  kilos,  or  289  cubic  meters  of  hydrogen,  while  a  like  weight 
of  clupanodonic  acid  with  its  four  double  bonds  requires  29  kilos,  or  348  cubic  meters 
of  hydrogen.  The  hydrogen  requirements  per  ton  of  some  of  the  fats  enumerated 
by  Sachs  are  as  follows: 

Cubic  meters 

Cocoanut  oil  ..............................................  7.8 

Tallow  ...................................................  33.57 

Olive  oil  ..................................................  68  .  80 

Oleic  acid  ..............................  .  ..................  88  .  80 

Corn  oil  ..................................................  143  .  75 

Dr.  Holde  observes  (Seifen.  Ztg.  (1912),  918)  that  oleic  acid,  the  most  important 
constituent  of  all  semi-drying  liquid  oils,  requires  only  2  parts  of  hydrogen  to  282 
parts  of  oil  in  order  to  get  stearic  acid,  while  linoleic  and  linolenic  acid  require 
4  and  6  parts  respectively  to  280  and  278  parts.  Ricinolic  acid,  which  contains  one 
atom  of  oxygen  more  than  oleic  acid,  forms  an  oxystearic  acid  which  has  a  very  high 
melting  point,  but  which  also  only  contains  2  atoms  more  of  hydrogen  than  the 
original  acid.  The  glycerides  of  stearic  or  palmitic  acid  naturally  remain  unchanged 
throughout  the  operation. 

t  According  to  Linde  (Production  of  Hydrogen,  Third  Int.  Cong,  of  Refrigeration, 
1913)  six  to  ten  cubic  meters  of  hydrogen  are  required  for  hardening  one  hundred 
kilos  of  oil. 

195 


Stearic  acid 


196  THE  HYDROGENATION  OF  OILS 

The  following  tabulation  shows  the  nature  of  the  reaction  in  several 
cases : 

Oleic  Acid Ci8H3402  +  2  H 

Linolic  Acid Ci8H32O2  +  4  H 

Linolenic  Acid Ci8H3oO2  +  6  H 

Clupanodonic  Acid Ci8H28O2  +  8  H 

(CisHssO^sCsHs  +  6  H          =          (CisHssO^sCsHB 
Olein  Stearin 

C22H42O2  +  2  H  C22H44O2 

Erucic  acid  Behenic  acid 

CigH^Os  +  2  H  =  CigHseOa 

Ricinoleic  acid  Hydroxystearic  acid 

One  of  the  problems  in  the  hydrogenation  field  is  that  of  a  cheap 
supply  of  pure  hydrogen.  The  demand  for  hydrogen  in  various 
directions  has  increased  of  late  and  undoubtedly  this  will  lead  to 
improvements  in  the  manufacture  of  the  gas. 

The  two  methods  now  most  favored  in  the  hydrogenation  of  oils 
are  the  iron-sponge  steam  process  and  the  electrolytic  method.  For 
large  plants  the  iron-sponge  steam  process  is  preferred,  but  it  is  rela- 
tively complicated  and  scarcely  to  be  recommended  for  plants  calling 
for  1000  cubic  feet  of  hydrogen,  or  less,  per  hour. 

In  the  electrolysis  of  brine  to  make  caustic  soda  and  bleach,  there 
exists  a  by-product  of  hydrogen  sufficient  in  amount  to  treat  an 
enormous  quantity  of  oil.  To-day  a  good  portion  of  this  hydrogen  is 
allowed  to  go  to  waste.  Eventually  it  may  be  used,  to  some  extent 
at  least,  for  hydrogenation  purposes.  One  electrolyic  plant  in  this 
country  is  producing  about  one  ton  of  hydrogen  daily.  Another 
plant  generates  nearly  one-half  a  ton,  while  a  third  concern  discharges 
into  the  air  nearly  300,000  cubic  feet  each  day.*  In  spite  of  the  vast 

*  Similar  conditions  exist  abroad,  Blum  reporting  (Met.  and  Chem.  Eng.  (1911), 
157)  that  enormous  amounts  of  hydrogen  gas  are  produced  in  the  large  works  for 
the  production  of  caustic  soda  and  chlorine  by  electrolysis  of  common  salt  solutions. 
The  hydrogen  gas  is  set  free  together  with  the  caustic  soda  at  the  cathode.  The 
quantities  are  so  large,  compared  with  the  demand  which  exists  at  present  for  hydro- 
gen, that  most  of  the  hydrogen  gas  is  passed  unused  into  the  air.  The  Griesheim- 
Elektron  Company  in  Germany  produces  daily  20,000  cubic  meters  of  hydrogen 
of  about  90  to  97  per  cent  purity.  In  this  case  the  cost  of  the  gas  is  practically 
that  of  its  compression  and  storage.  Special  railway  cars  are  built  in  Germany 
for  the  transportation  of  500  cylinders  containing  2750  cubic  meters  of  hydrogen 
gas.  The  cost  of  shipment  of  the  cylinders  is  so  great  that  the  distribution,  of 
course,  is  only  local,  as  regards  consumption  on  the  large  scale.  The  Zeppelin  Ga- 
rage in  Frankfort  is  supplied  with  hydrogen  by  means  of  a  high-pressure  main  from 
Griesheim. 


THE  HYDROGEN  PROBLEM  IN  OIL  HARDENING          197 

amount  of  by-product  hydrogen  obtainable,  it  appears  that  oil  manu- 
facturers prefer  to  install  hydrogen-generating  equipment  in  their 
present  works,  rather  than  to  ship  oil  to  a  source  of  waste  hydrogen 
and  conduct  hardening  operations  at  some  relatively  remote  point. 

In  consequence  the  present  methods  of  preparing  hydrogen  are  being 
carefully  scrutinized  and  new  systems  for  the  generation  of  the  gas 
are  being  studied  and  developed.  For  this  reason  the  whole  subject 
of  the  production  of  hydrogen  is  here  reviewed  at  some  length,*  the 
proposed  technical  methods  for  its  generation  being  classified  as 
follows : 

A.  Water  gas  as  a  source  of  hydrogen. 

1.  Replacement  of  carbon  monoxide  by  hydrogen. 

2.  Liquefaction  and  other  methods  for  the  removal  of  carbon 

monoxide. 

B.  Decomposition  of  hydrocarbons. 

C.  Action  of  steam  on  heated  metals. 

D.  Wet  processes  and  the  decomposition  of  hydrates. 

1.  Action  of  acids  on  metals. 

2.  Decomposition  of  water  by  miscellaneous  chemicals. 

3.  Electrolysis  of  water. 

4.  By-product  hydrogen. 

The  hydrogen  problems  involved  in  the  hydrogenation  of  oils  are 
discussed  by  Walter  f  who  states  that  a  plant  for  oil  hardening  cannot 
well  be  installed  by  small  concerns,  but  only  by  those  having  power- 
ful financial  resources,  because  the  cost  of  equipping  for  an  adequate 
supply  of  hydrogen  represents  so  great  an  outlay.  If  water  gas  or 
coke  oven  gas  containing  40  to  50  per  cent  hydrogen  could  be  used  the 
matter  would  present  a  different  aspect.  Water  gas  contains  on  the 
average : 

Per  cent 

Hydrogen 50 

Carbon  monoxide 41 

Carbon  dioxide 4 

Nitrogen 4.5 

Methane 0.5 

A  plant  for  the  manufacture  of  water  gas  is  much  cheaper  than  one 
for  making  technically  pure  hydrogen.  Reckoned  on  the  hydrogen 
content  the  cost  of  production  of  water  gas  is  very  much  lower  than 
that  of  pure  hydrogen. 

*  Brahmer,  Chemie  der  Gase,  Frankfort,  1911,  contains  much  useful  informa- 
tion on  the  production  of  hydrogen.  The  subject  of  hydrogen  production  on  a 
commercial  scale  is  treated  by  Lepsius  in  Moniteur  Scientifique,  1912,  493-500. 

t  Seifen.  Ztg.  (1913),-4. 


198  THE  HYDROGENATION  OF  OILS 

Coke  oven  gas  contains  about  the  following: 

Per  cent 

Hydrogen 46 

Nitrogen 15 

Carbon  monoxide 7 

Methane 20 

Ethylene 2 

Carbon  dioxide 4 

This  gas  may  be  obtained  in  large  quantities  at  low  cost  in  the  neighborhood  of 
coke  oven  plants.  Many  of  the  patents  relating  to  the  hydrogenation  of  oils  refer 
to  the  use  of  gas  mixtures  containing  hydrogen  as  well  as  to  hydrogen  gas  in  a  pure 
state.  These  statements,  Walter  argues,  appear  apparently  only  as  a  precaution  in 
order  to  preclude  others  from  making  application  for  patent  protection  on  the  use 
of  hydrogen-containing  gases  in  the  place  of  pure  hydrogen.  He  regards  the  investi- 
gation of  these  hydrogen-containing  mixtures  as  never  having  been  properly  followed 
out,  but  thus  far  the  results  obtained  are  not  promising. 

Carrying  out  the  hydrogenation  process  with  hydrogen-containing 
gases  involves:  (1)  the  catalyzer  must  not  become  contaminated 
with  poisons;  (2)  the  process  must  proceed  in  spite  of  the  presence 
of  foreign  gases;  (3)  foreign  gases  must  not  injure  the  oil. 

Carbon  monoxide  and  nitrogen  in  the  pure  state  apparently  do  not 
injure  the  usual  catalyzers  in  the  least.  As  to  the  remaining  impur- 
ities the  sulfur  compounds  are  catalyzer  poisons.  It  has  been  noted 
with  water  gas  that  the  catalyzer  loses  its  activity  much  sooner  than 
when  pure  hydrogen  is  employed.  Foreign  gases,  which  are  indiffer- 
ent in  a  chemical  sense,  of  course  dilute  the  hydrogen  with  which 
they  may  be  mixed,  and  when  one  is  working  with  a  dilute  in  place 
of  a  concentrated  reagent,  the  action  usually  is  slower.  In  this  con- 
nection investigation  shows  that  with  increasing  dilution  of  the  hydro- 
gen employed,  the  time  required  for  treatment  lengthens,  a  result 
which,  of  course,  ordinary  practice  would  indicate  is  to  be  expected. 
Also  hardening  cannot  easily  be  carried  as  far  with  hydrogen-contain- 
ing gases  as  with  pure  hydrogen.  It  can  be  stated  as  a  general  rule 
that  in  oil  hardening  the  hydrogen  conducted  into  the  oil  is  not  wholly 
absorbed,  but  goes  as  a  stream  of  gas  through  or  in  contact  with  the 
oil,  so  a  considerable  proportion  of  the  hydrogen  introduced  is  not 
used.  When  one  is  using  water  gas  in  place  of  hydrogen,  the  former 
gives  up  only  a  portion  of  its  hydrogen  to  the  oil.  The  hydrogen 
available  to  the  oil  is  thus  proportionately  less  than  with  ordinary 
hydrogen  gas,  and  repeated  conveyance  of  the  partially-used  water 
gas  through  the  oil  is  as  good  as  useless  because  of  the  great  reduc- 
tion in  the  proportion  of  hydrogen. 

Since  only  a  part  of  the  hydrogen  contained  in  water  gas  may  be 
utilized,  it  is  necessary  to  employ  relatively  a  much  larger  quantity 
of  the  latter.  Of  the  50  per  cent  or  so  of  hydrogen  contained  in 


THE  HYDROGEN  PROBLEM  IN  OIL  HARDENING          199 

water  gas,  according  to  Walter,  only  about  one-third  or  approximately 
17  per  cent  of  the  total  gas  is  used.  To  secure  the  same  effect  600 
cubic  feet  of  water  gas  in  place  of  100  cubic  feet  of  hydrogen  are  re- 
quired, in  which  case  about  500  cubic  feet  of  spent  gas  results.  The 
spent  gas,  of  course,  should  not  be  thrown  away  as  this  would  be 
wasteful  and  arrangements  must  be  made  for  its  use  in  heating, 
lighting  or  power  applications.  It  is  not  always  convenient  to  thus 
make  use  of  such  a  large  volume  of  hydrogen-spent  gas;  furthermore 
it  is  necessary  to  make  all  the  pipes  and  connections  larger  by  six- 
fold than  when  concentrated  hydrogen  is  employed,  which  means  an 
additional  expense. 

Finally  there  is  the  question  as  to  whether  or  not  the  foreign  gases  * 
contained  in  water  gas  exert  any  detrimental  influence  upon  the  har- 
dened oil;  whether  they  do  not  during  the  process  bring  about  side 
reactions.  As  regards  carbon  monoxide  f  and  carbon  dioxide  no 
chemical  action  on  oils  or  fatty  acids  under  these  conditions  is  known, 
yet  eventually  catalyzers  may  be  employed  which  cause  side  reactions. 
If  the  hardened  oil  is  to  be  used  for  technical  purposes  such  reactions 
probably  need  not  be  feared,  but  for  edible  purposes  this  may  not 
obtain.  In  this  connection  Bomer  has  laid  down  the  condition  in  oil 
hardening  that  the  hydrogen  employed  must  be  pure  when  the  fat  is 
to  be  used  for  edible  purposes.  Thus  when  using  water  gas  in  place 
of  hydrogen,  a  number  of  difficulties  are  likely  to  arise  in  large  scale 
operation  and  the  seeming  financial  advantage  on  close  inspection 
shrinks  considerably,  practically  leaving  the  field  to  technically  pure 
hydrogen.  { 

*  The  addition  of  small  quantities  of  a  second  gas  to  a  pure  gas  markedly  reduces 
the  rate  of  diffusion  in  liquids,  according  to  Barns  (Chem.  Abs.  (1913),  3871). 

f  Caro  (Seifen.  Ztg.  (1913),  852)  considers  the  presence  of  carbon  monoxide  in 
hydrogen  used  for  hardening  fats  with  nickel  catalyzers  to  be,  under  some  circum- 
stances, injurious  to  the  catalyzer.  Maintaining  the  temperature  of  the  oil  during 
hydrogenation  above  200°  C.  is  said  to  be  beneficial,  as  any  nickel  carbonyl  formed 
will  be  at  once  decomposed  at  that  temperature. 

I  The  importance  of  the  problem  of  securing  hydrogen  in  large  quantities  is 
evidenced  by  an  order  recently  placed  by  an  American  oil  concern  for  2  gasometers 
to  hold  hydrogen,  each  said  to  have  a  capacity  of  about  1,000,000  cubic  feet  of  the 
gas. 

Goldschmidt  (Seifenfabr.,  32,  713)  states  that  a  good  and  cheap  source  of  hydro- 
gen gas  is  one  of  the  greatest  problems  connected  with  the  process;  that  such 
impurities  in  the  gas  as  arsenic,  phosphorus,  hydrogen  sulfide,  mineral  acids,  carbon 
bisulfide,  chloroform  and  acetone  poison  catalysts  of  the  platinum  group;  while 
sulfur,  chlorine,  bromine  and  iodine  unfavorably  affect  those  of  the  nickel  group. 

Fry  states  that  negative  hydrogen  has  been  shown  to  act  as  a  reducing  agent, 
since  it  naturally  tends  to  revert  to  its  ordinary  state,  positive  hydrogen,  which 
change  is  accompanied  by  the  liberation  of  electrons.  (J.  S.  C.  I.,  1914,  271.) 


CHAPTER  XIII 

WATER   GAS  AS  A  SOURCE   OF  HYDROGEN  AND   THE 

REPLACEMENT   OF   CARBON   MONOXIDE 

BY  HYDROGEN 

Many  suggestions  have  arisen  for  the  production  of  hydrogen  from 
water  gas,  involving  replacement  of  the  carbon  monoxide  present  by 
hydrogen  through  the  reaction 

CO  +  H20  =  C02  +  H2. 

Because  of  the  incompleteness  of  the  reaction,  those  methods  proposed 
which  do  not  take  cognizance  of  the  accumulation  of  carbon  dioxide 
and  consequent  repression  of  the  progress  of  the  reaction  have  not 
been  particularly  successful.  The  reaction  is  a  reversible  one  and 
unless  means  are  taken  to  remove  the  carbon  dioxide  as  formed,  the 
resulting  gas  mixture  contains  hydrogen,  carbon  dioxide  and  carbon 
monoxide  usually  in  such  proportion  as  to  be  too  costly  of  purification 
for  handling  on  the  large  scale.  In  consequence  lime  or  other  alkali 
has  been  suggested  for  absorbing  the  carbon  dioxide.  These  sugges- 
tions appear  in  the  patents  to  Tessie  Du  Motay  and  the  Chemischen 
Fabrik  Greisheim-Elektron,  as  will  be  pointed  out  in  a  more  detailed 
manner  in  the  following. 

Engels  *  has  made  a  careful  study  of  the  reaction  between  carbon 
monoxide,  water  vapor  and  lime.  The  investigations  show  that  the 
most  suitable  temperature  lies  between  450°  to  550°  C.  Below  450°  C. 
the  reaction  progresses  too  slowly,  while  above  550°  C.  the  conversion 
does  not  go  to  completion  or  side  reactions  occur.  Engels  studied  the 
effect  of  additions  of  an  oxide,  such  as  iron  oxide,  to  the  lime  in  order 
to  catalytically  hasten  the  reaction  and  found  its  course  to  be  much 
improved  by  the  addition  of  a  few  per  cent  of  such  catalyzer.  The 
reaction  is  exothermic  so  no  further  external  heating  is  necessary  after 
the  conversion  has  begun. 

In  1880  Tessie  du  Motay  devised  a  process  for  the  production 
of  hydrogen  from  water  gas.f  The  latter  gas  mixed  with  steam  is 

*  Uber  die  Wasserstoffgewinnung  aus  Kohlenoxyd  und  Kalkhydrat,  Disserta- 
tion, Karlsruhe,  1911. 

t  U.  S.  Patents  229,338,  229,339  and  229,340,  June  29,  1880. 

200 


WATER  GAS 


201 


passed  into  a  converter  containing  lime  where  hydrogen  and  calcium 
carbonate  are  formed.  Fig.  57  shows  a  plan  view  of  the  apparatus, 
in  which  A  is  a  water-gas  generator,  B  represents  purifiers  in  which 


FIG.  57. 


sulfur  is  removed,  C  designates  superheaters  where  steam  is  mixed 
with  the  water  gas.  The  preheated  mixture  then  passes  to  a  converter 
shown  in  Fig.  58.  The  inclined 
passageways  of  the  latter  are 
filled  with  lime  in  contact  with 
which  the  reaction 

CO  +  H20  =  C02  +  H2 

CO2  +  CaO  =  CaCO3, 

progresses,  yielding  hydrogen 
gas.  In  lieu  of  water  gas,  coal 
gas  or  the  vapor  of  naphtha 
may  be  similarly  treated. 

The  process  of  the  Chem. 
Fabrik  Greisheim-Elektron,  re- 
ferred to  above,*  involves  mix- 
ing water  gas  with  an  excess  of 
steam  and  passing  this  mixture  over  lime  or  hydrated  lime  to  which 
about  5  per  cent  of  iron  powder  has  been  added.  The  lime  is  heated 
to  approximately  500°  C.  in  an  upright  retort  fitted  with  an  agitator. 
The  following  reaction  takes  place: 

Ca  (OH),  +  CO  =  CaCO3  +  H2, 
*  Zeitsch.f.  angew.  Chem.  (1912),  2401;  British  Patent  2523,  Feb.  2,  1909. 


FIG.  58. 


202  THE  HYDROGENATION  OF  OILS 

with  evolution  of  heat,  and  the  reaction  chamber  is  cooled  so  that 
the  temperature  does  not  exceed  500°  C.,  or  the  temperature  at  which 
calcium  carbonate  commences  to  dissociate.  The  carbonate  is  re- 
generated by  subsequent  calcination.*  The  presence  of  water  vapor 
or  of  lime  in  the  hydrated  condition  is  essential  for  the  reaction. f 
If  absent  or  present  in  insufficient  quantities  the  carbon  monoxide 
is  absorbed  by  the  lime  without  the  formation  of  hydrogen.  In  the 
absence  of  water  the  reaction  runs  according  to  the  following  equation : 
CaO  +  2  CO  =  CaC03  +  C. 

According  to  the  statement  of  Lepsius  hydrogen  of  97.5  per  cent 
purity  is  obtained  at  a  cost  of  about  2  to  2.5  cents  per  cubic  meter. 

The  production  of  hydrogen  by  the  action  of  carbon  monoxide  and 
steam  on  quicklime  is  regarded  by  Levi  and  Piva  I  to  be  dependent  on 
the  intermediate  formation  of  calcium  formate. 

Merz  and  Weith  §  have  noted  that  when  moist  carbon  monoxide 
is  passed  over  soda  lime  heated  to  300°  C.  or  over,  hydrogen  is  formed. 
A  simple  process  for  the  production  of  hydrogen  based  on  the  observa- 
tions of  Merz  and  Weith  has  been  put  forward  by  the  Societe  generate 
des  Nitrures  in  Paris.  A  mixture  of  producer  gas  and  water  gas  is 
treated  in  the  usual  way  to  remove  carbon  dioxide  and  is  then  passed 
over  hot  lime,  which  treatment  yields  a  mixture  of  nitrogen  and  hydro- 
gen free  from  carbon  monoxide.  The  composition  of  the  hydrogen- 
nitrogen  mixture  may  be  adjusted  by  using  different  proportions  of 
the  producer  gas  and  water  gas.|| 

Jerzmanowski  ^[  makes  a  hydrogen-containing  gas  with  apparatus  shown  in  Fig.  59. 

A  kiln  B  filled  with  lime  is  raised  to  a  high  temperature  by  burning  producer  gas 
from  the  generator  A.  As  soon  as  a  sufficient  heat  is  attained  in  B,  an  injector  H 
blows  into  B  steam  and  petroleum,  which  are  decomposed  chiefly  into  hydrogen 
and  carbonic  acid  along  with  small  quantities  of  carbonic  oxide,  marsh  gas  and 
other  impurities.  The  gases  pass  through  a  cooler  C  to  the  gasometer  D,  and  thence 
to  purifiers.** 

*  The  Chemische  Fabrik  Griesheim-Elektron  (British  Patent  13,049,  June  3,  1912) 
mix  steam  with  gas  containing  carbon  monoxide  and  pass  the  mixture  upwards 
through  towers  packed  with  pieces  of  lime  and  heated  to  between  400°  and  700°  C. 
The  lime,  when  exhausted  owing  to  conversion  into  calcium  carbonate,  can  be  re- 
generated in  situ  by  diverting  the  stream  of  gases  and  recalcining. 

t  U.  S.  Patent  989,955,  April  18,  1911,  to  Ellenberger,  assigned  to  the  Chemische 
Fabrik  Griesheim-Elektron,  discusses  these  reactions. 

t  J.  S.  C.  I.,  1914,  310. 

§  Ber.  (1880),  719.     See  also  Ber.  1880,  31. 

li  Sander,  Zeitsch  f.  angew.  Chemie  (1912),  2406. 

H  J.  S.  C.  I.,  1884,  560. 

**  The  New  York  Oxygen  Company  produce  hydrogen  by  heating  together  anthra- 
cite and  slaked  lime.  On  passing  an  excess  of  steam  over  the  residue  in  the  retorts 
the  reverse  action  sets  in  and  the  slaked  lime  is  reproduced.  This  sequence  may  be 
continued  many  times  without  renewing  the  materials.  (J.  S.  C.  I.,  1887,  92.) 


WATER  GAS 


203 


By  another  process  steam  is  allowed  to  act  on  carbon  or  carbonaceous  matter 
to  which  both  an  alkali  compound  and  lime  have  been  added,  the  effect  of  the  addi- 
tions according  to  Dieffenbach  and  Moldenhauer  (British  Patent  8734,  April  11, 
1910)  being  to  lower  the  temperature  of  decomposition  and  to  give  hydrogen  free 
from  compounds  of  carbon  and  oxygen.  For  example,  100  kilos  of  charcoal  or  coke, 
impregnated  with  a  10  per  cent  solution  of  potassium  carbonate,  are  mixed  with 
500  kilos  of  quicklime,  and  the  mixture  is  decomposed  by  steam  at  550°  to  750°  C. 


FIG.  59. 


They  also  claim  (British  Patent  7718,  March  30,  1910)  the  employment  of  other 
alkali  compounds  —  such  as  chlorides  and  sulfates  —  for  the  same  purpose.  The 
fuel  is  impregnated  with  a  solution  of  the  alkali  compound  and  dried,  or,  if  practical, 
the  fuel  is  coked  after  the  addition  of  such  compound.  A  comparatively  small 
amount  of  oxygen  may  be  introduced  along  with  the  steam  for  the  purpose  of  main- 
taining the  required  temperature  inside  the  decomposition  apparatus.  Granulated 
coal  or  coke  may  be  treated  with  a  solution  of  an  alkali  silicate  or  carbonate  and  the 
mixture  briquetted  and  subjected  to  the  action  of  superheated  steam  at  temperatures 
from  550°  to  750°  C.* 

Hembert  and  Henry  f  pass  superheated  steam  in  a  fine  spray  over 
coke  heated  to  redness,  whereby  a  mixture  of  hydrogen  and  carbon 
monoxide  is  formed.  This  mixture  is  led  into  a  second  retort  filled 
with  fireproof  materials,  also  heated  to  redness.  In  the  second 
retort  steam  is  allowed  to  enter  heated  to  its  point  of  dissociation. 
These  gases  act  upon  one  another,  hydrogen  and  carbon  dioxide  being 
formed.  The  carbon  dioxide  may  be  absorbed  by  milk  of  lime.  In 
this  way  3200  cubic  meters  hydrogen  are  said  to  be  obtained  from 
1  ton  of  coke. 

In  the  production  of  a  mixture  of  hydrogen  and  carbon  dioxide  by  the  action  of 
steam  on  carbonaceous  substances  or  on  water  gas,  Sauer  (German  Patent  224,862, 
May  9,  1907)  proposes  to  use  an  excess  of  steam  and  to  superheat  this  to  such  a 
degree  that  it  suffices  to  maintain  the  proper  reaction  temperature,  in  order  to 
ensure  the  production  of  a  gas  of  uniform  composition.  For  example  in  the  action 
of  steam  on  coal,  the  latter  is  not  blown  alternately  with  air  and  steam,  but  the 

*  French  Patent  417,929,  April  25,  1910. 
t  Compt.  Rend.  (1885),  101,  797. 


204  THE  HYDROGENATION   OF  OILS 

steam  is  superheated  to  such  a  degree  that  when  the  process  is  once  started  it  is 
supposedly  carried  on  continuously  by  aid  of  the  heat  of  the  steam  alone.* 

For  treating  hydrogen  and  carbon  compounds  to  oxidize  the  carbon 
to  carbonic  acid,  in  which  form  it  may  be  readily  eliminated,  leaving 
pure  hydrogen,  Moore  f  brings  the  hydrogen  and  carbon  compounds 
in  a  suitably  divided  state  (generally  as  a  gas  or  fine  spray)  into  con- 
tact with  heated  oxide  of  iron,  manganese,  copper,  tin,  lead  or  zinc, 
in  the  presence  of  a  jet  of  superheated  steam.  During  the  operation 
the  oxides  are  said  to  be  alternately  reduced  and  reoxidized,  acting  as 
carriers  of  oxygen  between  the  steam  and  the  carbon  compounds,  so 
that  the  carbon  present  is  converted  into  carbon  dioxide,  and  leaves 
the  chamber  in  which  this  is  effected  mixed  with  the  hydrogen  origi- 
nally present  and  that  resulting  from  the  decomposition  of  the  steam. 
The  carbon  dioxide  may  be  removed  by  any  known  method,  such  as 
absorption  by  lime,  or  by  water  under  pressure,  or  by  a  solution  of 
alkaline  carbonate. 

Mond  and  Langer  (British  Patent  12,608,  Sept.  1,  1888)  bring  carbonic  oxide  or 
gaseous  hydrocarbons  into  contact  with  metallic  nickel  at  a  temperature  of  350°  to 
400°  C.,  or  with  metallic  cobalt  at  400°  to  450°  C.,  when  decomposition  takes  place 
into  carbon  and  carbonic  acid  or  hydrogen,  the  carbon  combining  with  the  metal. 
If  now  steam,  at  a  moderate  temperature,  be  introduced  this  carbon  combines  with 
oxygen  to  produce  carbonic  acid,  with  simultaneous  formation  of  free  hydrogen. 
These  various  reactions  take  place  simultaneously  when  the  steam  is  passed  through 
the  apparatus  along  with  the  carbonic  oxide  or  hydrocarbon,  the  ultimate  products 
being  carbonic  acid  and  hydrogen.  The  former  can  be  eliminated  by  any  suitable 
means,  such  as  by  washing  with  milk  of  lime.  The  cobalt  or  nickel  surfaces  may 
be  obtained  by  impregnating  pumice  stone  with  a  solution  of  the  metal,  and  reducing. 

Similarly  Elworthy  J  heats  a  mixture  of  water  gas  and  steam  in  the 
presence  of  such  metals  as  nickel  or  iron  to  a  sufficiently  high  temper- 
ature to  induce  the  reaction, 

C0  +  H20  = 


whereby  the  hydrogen  originally  present  in  the  water  gas  is  increased 
by  a  volume  equal  to  that  of  the  carbon  monoxide  contained  in  it. 
The  resulting  carbon  dioxide  is  removed  by  absorption  by  water  under 
pressure,  or  by  alkalis,  or  by  other  known  means. 

Ellis  and  Eldred  §  generate  a  hydrogen-containing  gas  as  follows: 

*  Green  (British  Patent  13,510,  July  13,  1895)  states  he  obtains  hydrogen  from 
water  by  an  improved  process,  "which  consists  in  burning  steam  with  hydrogen  gas, 
or  with  carburetted  hydrogen,  or  carbon  monoxide  within  a  suitable  chamber." 

t  J.  S.  C.  I.,  1885,  450. 

%  French  Patent  355,324,  June  17,  1905. 

§  U.  S.  Patent  854,157,  May  21,  1907. 


WATER  GAS  205 

Producer  gas,  generated  by  blowing  air  through  a  producer  charged 
with  fuel,  is  led  through  a  superheating  chamber  filled  with  checker- 
work  of  refractory  material.  The  gas  is  then  passed  under  a  boiler 
and  burned  to  generate  steam.  Water  gas  is  mixed  with  steam  and 
passed  through  the  superheater  to  convert  the  carbon  monoxide  into 
dioxide.  The  mixture  of  carbon  dioxide  and  hydrogen  is  then  com- 
pressed; the  former  is  separated  in  the  liquid  condition  and  the  latter 
is  collected  separately.  The  process  is  rendered  continuous  by  repeat- 
ing the  above  steps  alternately.* 

The  essential  feature  of  a  process  devised  by  Dieffenbach  and 
Moldenhauer  f  is  that  a  mixture  of  steam  with  a  hydrocarbon  or 
other  suitable  organic  compound  is  heated  to  the  temperature  of 
reaction,  or  kept  in  contact  with  a  catalytic  body  for  only  a  short 
time  and  is  then  suddenly  cooled  or  removed  from  the  catalyzer,  in 
order  that  the  carbon  dioxide  formed  shall  have  little  or  no  opportu- 
nity for  being  reduced  to  carbon  monoxide.  From  the  resulting  mix- 
ture of  hydrogen  and  carbon  dioxide,  the  latter  can  easily  be  removed, 
leaving  more  or  less  pure  hydrogen.  A  suitable  way  of  carrying  out 
the  process  is  to  use  as  catalyzer  wire  gauze  of  nickel,  cobalt,  platinum, 
etc.,  disposed  transversely  to  the  direction  of  flow  of  the  gases,  and 
heated  electrically  to  the  requisite  temperature.  Instead  of  using 
external  heating,  the  required  temperature  may  be  attained  partly 
or  entirely  by  combustion  of  a  portion  of  the  hydrocarbon  by  means 
of  admixed  oxygen. 

Naher  and  Muller  J  prepare  water  gas  by  blowing  superheated 
steam  into  a  generator  filled  with  coke,  which  has  been  heated  to 
about  1000°  C.,  and  exhausted,  and  the  gas  produced,  mixed  with 
superheated  steam,  is  passed  over  a  contact  mass  of  rhodium-  or  palla- 
dium-asbestos at  800°  C.  The  resulting  hydrogen  then  is  freed  from 
the  accompanying  carbon  dioxide. 

Carbon  monoxide  and  steam  are  caused  to  interact  at  300°  to 
600°  C.  under  a  pressure  of  4  to  40  atmospheres  in  the  presence  of  a 
catalyst,  such  as  iron,  nickel,  or  the  like,  with  the  production  of 
carbon  dioxide  and  hydrogen,  the  former  being  removed  by  absorp- 
tion according  to  a  process  devised  by  the  Badische  Company. § 

In  order  to  better  effect  the  reaction  betweeen  carbon  monoxide 
and  water  vapor  in  the  presence  of  heated  catalytic  material  and  to 
carry  on  the  operation  continuously  the  Badische  Company  inject 

*  Ellis  and  Eldred  employ  nickel,  iron  or  manganese  as  catalytic  material. 
f  German  Patent  229,406,  June  3,  1909. 
t  German  Patent  237,283,  Sept.  30,  1910. 
§  British  Patent  26,770,  Nov.  21,  1912. 


206  THE  HYDROGENATION  OF  OILS 

oxygen  or  air  into  the  reaction  chamber  thus  securing  the  necessary 
heating  effect.* 

Pullman  and  Elworthy  f  generate  a  mixture  of  hydrogen  and  car- 
bon dioxide  by  passing  superheated  steam  in  excess  over  red-hot  coke 
or  charcoal  contained  in  a  cast-iron  retort,  and  the  mixed  gases  after 
cooling  are  led  through  a  number  of  porous  pipes  made  of  plaster  of 
Paris  or  unglazed  earthenware  where  they  are  separated  to  a  great 
extent  by  diffusion,  the  hydrogen  passing  more  rapidly  through  the 
porous  walls  of  the  pipes  than  the  carbon  dioxide. 

After  leaving  the  diffusing  apparatus  the  nearly  pure  hydrogen  is  compressed 
into  suitable  vessels  partially  filled  with  water  to  absorb  most  of  the  remaining  carbon 
dioxide.  On  opening  the  valves  of  the  vessels  the  hydrogen  rapidly  escapes,  and 
may  be  collected  in  a  suitable  holder  and  then  given  a  final  purification,  either  by 
washing  with  water  in  a  scrubber  or  by  passing  it  over  some  absorbent  for  carbonic 
acid,  such  as  damp  hydrate  of  lime,  or  through  milk  of  lime.  Instead  of  separating 
the  mixed  gases  by  diffusion,  they  may  be  taken  from  the  cooling  apparatus  direct 
and  compressed  in  strong  metal  vessels  partially  filled  with  water.  The  carbonic 
acid  being  much  the  more  soluble,  on  opening  the  vessels  hydrogen  at  first  escapes 
rapidly  and  may  be  collected,  the  carbonic  acid  being  afterwards  collected  in  a 
separate  receiver.  The  gases  may  be  submitted  to  this  operation  several  times  over, 
and  finally  purified  as  above.  Or  instead  of  using  water,  glycerine  or  hydrocarbon 
oils  which  absorb  more  gas  and  part  with  it  more  slowly  may  be  used. 

That  complete  replacement  of  carbon  monoxide  by  hydrogen  in  processes  in- 
volving heating  water  gas  and  steam  is  impossible  because  of  the  conditions  of  equilib- 
rium which  obtain,  is  discussed  by  Gautier  (Bull.  Soc.  Chim.  (1906),  35,  929)  who 
refers  to  the  work  of  Boudouard  (Bull.  Soc.  Chim.  (1901),  25,  484).  The  latter 

CO 
determined  the  ratio  7^-,  in  the  equilibrium  between  carbon  monoxide,  steam,  carbon 


dioxide,  and  hydrogen  at  different  temperatures;  and  Hahn  (Z.  Physik  Chem.  (1903), 

CO  v  TT  O 

42,   705;  44,   513;   (1904),  48,  735)   determined  the  coefficient  K  =     "     J"  !;   > 

v^v>'2    X  X12 

at  different  temperatures.  When  a  current  of  carbon  monoxide  mixed  with  a  vary- 
ing excess  of  steam  is  passed  through  a  porcelain  tube  heated  to  1200°  to  1250°  C., 
at  the  rate  of  about  1  liter  of  the  mixed  gases  per  hour,  or  when  a  dry  mixture  of 
equal  volumes  of  carbon  dioxide  and  hydrogen  is  similarly  treated  at  1300  degrees, 
the  reaction  proceeds  until  the  volume  of  hydrogen  is  about  double  that  of  carbon 
monoxide.  The  reactions  correspond  with  the  equations: 

3  CO  +  3  H2O  =  CO  +  H2O  +  2  H2  +  2  CO2, 
3  CO2  +  3  H2     =  CO  +  H2O  +  2  H2  +  2  CO2. 

Under  these  conditions,  any  mixture  of  carbon  monoxide,  steam,  hydrogen  and 
carbon  dioxide  tends  towards  the  composition,  CO  +  H2O  +  2  H2  +  2  CO2.  Small 
quantities  of  formic  acid,  but  no  formaldehyde,  are  produced. 

Additional  matter  by  Gautier  appears  in  Comptes  rendus  (1910),  150,  1564, 
considering  the  reaction  particularly  from  the  reverse  standpoint,  that  is,  the  reduc- 

*  British  Patent  27,117,  Nov.  25,  1912;  Chem.  Zeit.  Rep.  (1913),  696. 
t  British  Patent  22,340,  Dec.  21,  1891. 


WATER  GAS  207 

tion  of  carbon  monoxide  by  hydrogen.  The  results  show  that  by  heating  carbon 
monoxide  in  the  presence  of  hydrogen,  water  is  actually  formed.  The  reduction 
begins  approximately  at  200°  C.  The  maximum  formation  of  water  is  between 
1100°  and  1200°  C.* 

By  a  process  of  the  Badische  Company  f  water  gas  is  passed  with 
an  excess  of  steam  over  heated  finely-divided  metals  of  the  iron 
group,  especially  iron,  cobalt  and  nickel,  or  their  oxides,  and  the  car- 
bon dioxide  formed  is  eliminated  from  the  gaseous  reaction  product. 
The  catalyst  is  best  prepared  by  the  addition  of  appropriate  diluents 
or  binding  agents,  organic  or  inorganic,  which  may  be  such  as  to  give 
off  gas  on  heating  so  as  to  increase  the  porosity.  For  example,  dry 
precipitated  ferrous  carbonate  may  be  made  into  a  plastic  mass  with 
lime,  water,  potassium  hydroxide  and  ferric  nitrate,  and  the  mix- 
ture dried  and  heated  to  500°  C.  A  reaction  temperature  of  prefer- 
ably not  over  600°  C.  is  maintained  by  adjusting  the  temperature  of 
the  gases  before  they  enter  the  contact  chamber. 

*  Met.  and  Chem.  Eng.  (1911),  511. 
t  French  Patent  459,918,  July  2,  1913. 


CHAPTER   XIV 

LIQUEFACTION   AND   OTHER   METHODS   FOR   THE 
REMOVAL   OF   CARBON   MONOXIDE 

As  uncarburetted  or  blue  water  gas  consists  of  approximately  equal 
parts  hydrogen  and  carbon  monoxide  with  small  amounts  of  other 
gases,  much  attention  has  been  given  to  methods  of  eliminating  the 
monoxide  by  solution,  absorption  and  liquefaction.  The  cost  of 
removal  of  the  carbon  monoxide  by  solvents  such  as  cuprous  chloride 
and  the  like  appears  to  be  too  great  for  commercial  application.  As 
the  monoxide  is  relatively  easily  liquefied  by  cold  and  pressure,  while 
hydrogen  is  extremely  resistant  to  liquefaction  under  like  conditions, 
processes  have-been  devised  for  removing  carbon  monoxide  in  this  way. 
As  a  source  of  cheap  hydrogen  this  method  offers  attractive  possi- 
bilities to  concerns  requiring  large  amounts  of  the  gas.  For  small 
plants  the  relatively  high  cost  of  installation  renders  the  use  of  lique- 
faction processes  less  feasible. 

The  pioneer  work  connected  with  the  development  of  the  lique- 
faction system  towards  a  commercial  goal  should  be  credited  to  C.  E. 
Tripler,  who  apparently  was  the  first  to  devise  methods  and  apparatus 
for  large  scale  liquefaction  of  air  and  other  gases.  In  1893  Tripler 
patented  *  the  method  of  condensation  "  of  a  current  of  gas  by  ex- 
pansion of  itself  over  the  conduit  through  which  it  passes."  On  this 
idea  is  based  the  present  systems  of  separating  hydrogen  and  carbon 
monoxide  through  liquefaction  of  the  latter. 

The  principle  of  liquefaction  by  compression  with  counter-current 
cooling  is  shown  diagrammatically  in  Fig.  60.  The  reducing  valve  R 
is  so  arranged  that  on  the  side  carrying  the  receiver  B  for  the  liquefied 
product  a  pressure  of  20  atmospheres  is  maintained,  while  on  the  other 
side  the  pressure  is  held  at  200  atmospheres.  The  operation  is  as 
follows.  Air  is  drawn  from  B  by  the  compressor  K,  passing  through 
the  outer  concentric  tube  of  the  coil.  After  compression  to  200  at- 
mospheres the  air  enters  the  cooler  KG  where  the  heat  generated  by 
compression  is  absorbed.  The  cooled  compressed  air  flows  through 
the  inner  tube  of  the  coil  to  the  reducing  valve  R  where  it  is  released 

*  British  Patent  4210,  1893. 
208 


LIQUEFACTION 


209 


at  20  atmospheres.     Circulation  in  this  manner  is  kept  up  until  the 
temperature  is  lowered  to  the  point  of  liquefaction. 

Nitrogen  boils  at  —  193  degrees,  carbon  monoxide  at  —  190  degrees 
and  carbon  dioxide  at  —  78  degrees  while  hydrogen  boils  at  —  252  de- 
grees and  may  easily  be  retained  in  gaseous  form  at  temperatures 
which  convert  the  other  components  of  water  gas  to  liquids  or  solids.* 


FIG.  60. 

Apparatus  in  various  forms  has  been  devised  by  Linde,  f  Claude,  Hildebrandt  and 
others  for  the  separation  of  the  components  of  mixed  gases  by  the  liquefaction  of 
the  more  easily  liquefied  constituents.  The  Hildebrandt  system,  shown  in  Fig.  61, 
consists  of  a  coil  of  pipe  of  relatively  large  diameter  through  which  two  smaller  pipes 
extend.  The  latter  are  indicated  by  1  and  7  in  the  upper  right-hand  terminus  of 
the  large  coil.  Gas  under  the  requisite  high  pressure  enters  at  1,  passes  along  one 
of  the  small  pipes  within  the  larger  pipe  of  the  large  coil,  emerges  at  2  and  passes 
along  the  central  riser  to  the  expansion  chamber  E.  Expansion  with  liquefaction 
occurs  here.  The  liquefied  product  flows  through  3  into  the  chamber  R  and  from 
thence  into  a  multiple  evaporating  coil  4,  which  consists  of  four  coiled  pipes  having 
openings  along  their  upper  sides.  Evaporation  of  the  more  easily  boiling  constitu- 
ents takes  place  as  the  product  flows  downwardly  along  the  evaporating  conduits. 
The  vaporized  portion  departs  through  the  perforations  of  the  coil  and  passes  through 
5  into  the  large  pipe  A,  moving  along  this  pipe  as  a  current  counter  to  the  high-pressure 
gas  entering  at  1  and  passing  out  of  the  system  by  the  horizontal  pipe  shown  on  the 
upper  right  hand.  The  liquid  fraction  collecting  in  G  flows  along  one  of  the  narrow 
pipes  to  2,  thence  through  one  of  the  narrow  pipes  in  the  large  coil,  upwardly  and 
out  at  7. 

*  The  production  of  hydrogen  by  liquefaction  is  clearly  described  by  Linde  in 
the  Proceedings  of  the  Third  Int.  Congress  of  Refrigeration,  1913.  See  also  a  very 
comprehensive  treatise  entitled,  "Lowest  Temperatures  in  Industry,"  issued  by 
Gesellschaft  fur  Lindes  Eismaschinen,  Munich. 

t  In  a  publication  entitled  "Lowest  Temperatures  in  Industry,"  it  is  stated  that 
five  plants  have  been  supplied  by  the  Linde  Co.  for  fat-hardening  purposes  and  that 


210 


THE  HYDROGENATION   OF  OILS 


Linde  makes  note  *  that  Frank  and  Caro,  with  the  aid  of  the  Linde 
firm,  have  succeeded  in  the  production  of  hydrogen  of  a  high  degree 
of  purity  from  water  gas.  Figs.  62  and  63  show  the  apparatus  dia- 
grammatically. 


FIG.  61. 


FIG.  62. 


FIG.  63. 


Compressed  water  gas  enters  by  the  innermost  tube  A,  and  is  cooled 
by  expansion  through  the  valves  and  return  of  the  cooled  gases  by  the 
middle  and  outermost  tubes  G  and  E  respectively,  until  liquefaction 
of  the  carbon  monoxide  occurs;  separation  then  takes  place,  the 
gaseous  hydrogen  escaping  through  the  valve  F  and  the  tube  G,  the 
liquid  carbon  monoxide  passing  through  the  valve  D  and  evaporating 

the  total  capacity  of  these  is  over  1000  cubic  meters  per  hour.     A  plant  in  St.  Peters- 
burg uses  100  cubic  meters;  another  in  Nishnj-Nowgorod  30  cubic  meters;  Bremen- 
Bersigheimer  Olfabriken  200  cubic  meters;   United  Soap  Works,  Ltd.,  Rotterdam, 
200  cubic  meters;  and  Ardol  Co.,  Leeds,  500  cubic  meters  per  hour. 
*  J.  S.  C.  I.,  1911,  746. 


LIQUEFACTION  211 

in  the  middle  tube.  It  was  found  impossible  to  liquefy  the  carbon 
monoxide,  however,  by  the  small  amount  of  cooling  by  internal  work 
of  a  gas  containing  so  much  hydrogen,  and  the  cooling  was  therefore 
aided,  as  indicated  in  Fig.  63,  by  cold-jacketing  the  lower  portion  of 
the  apparatus  by  means  of  a  similar  apparatus  producing  liquid  air; 
in  this  way  the  industrial  success  of  the  apparatus  was  secured,  and 
a  gas  produced,  containing  hydrogen,  97  per  cent;  carbon  monoxide, 
2  per  cent;  nitrogen,  1  per  cent.  Removal  of  the  carbon  monoxide  by 
calcium  carbide  or  soda  lime  then  yields  a  99  per  cent  hydrogen.  The 
gas  formed  from  the  liquid  contains  85  to  90  per  cent  of  carbon  mon- 
oxide, the  rest  being  chiefly  hydrogen,  and  is  an  excellent  power  gas. 

By  one  process  (Ges.  fur  Linde's  Eismaschinen  A.  G.,  French  Patent  427,983, 
March  31,  1911)  the  strongly-cooled,  compressed  gaseous  mixture  containing  hydro- 
gen is  passed  through  a  heat  interchanger  so  as  to  separate  it  into  a  gaseous  portion, 
chiefly  hydrogen,  and  a  liquid  portion,  consisting  mainly  of  impurities.  The  mix- 
ture passes  into  a  receiver,  which  is  provided  with  two  separate  systems  for  producing 
expansion;  the  liquid  portion  of  the  mixture  collects  in  the  receiver  and  is  expanded 
in  the  lower  system,  from  which  it  passes  into  the  interchanger  in  the  space  sur- 
rounding the  tube  which  conveys  the  original  mixture  into  the  receiver,  and  in  the 
opposite  direction  to  that  of  the  gaseous  current;  the  gaseous  portion  is  expanded 
in  the  upper  system  and  passed  into  the  interchanger  in  the  space  surrounding  the 
tube  which  conveys  the  mixture  expanding  from  the  lower  system.  From  the  inter- 
changer the  expanded  hydrogen  is  collected  free  from  impurities,  which  are  thus 
condensed  by  the  cold  produced  by  the  agency  of  the  above-mentioned  expansions. 
A  supplementary  refrigerating  appliance,  containing  liquid  air  or  liquid  nitrogen, 
is  used  in  conjunction  with  the  apparatus  for  the  preliminary  cooling  of  the  gaseous 
mixture. 

A  modified  form  of  the  foregoing  consists  in  removing  the  portion  of  the  gaseous 
mixture  which  is  not  liquefied,  and  comprises  chiefly  hydrogen,  without  allowing 
it  to  expand,  the  pressure  remaining  equal  to  that  to  which  the  compressed  gaseous 
mixture  has  been  brought.  Liquid  air  or  liquid  nitrogen,  used  for  refrigeration, 
is  evaporated  at  a  pressure  below  that  of  the  atmosphere,  in  order  to  obtain  a  more 
complete  separation  of  the  remaining  impurities.  The  liquid  air  or  liquid  nitrogen  is 
thus  used  only  for  the  ultimate  refrigeration  of  the  hydrogen  which  has  already  been 
freed  from  the  main  quantity  of  condensable  gases.  Also,  the  hydrogen,  before  it  is 
brought  to  the  expansion  apparatus  may  be  subjected  to  slight  heating  in  a  counter- 
current  device,  by  means  of  the  compressed  gaseous  mixture  which  has  not  yet 
been  fractionated.* 

Frank  f  cools  water  gas  in  a  suitable  apparatus  sufficiently  to  liquefy 
the  carbon  monoxide  and  dioxide,  which  are  then  separated.  If  the 
water  gas  has  been  produced  at  a  low  temperature,  and  contains 

*  Ges.  fur  Linde's  Eismaschinen  A.  G.,  First  Addition,  to  French  Patent  427,983, 
March  31,  1911.  See  also  U.  S.  Patents  to  Carl  von  Linde  1,020,102  and  1,020,103, 
March  12,  1912;  1,027,862  and  1,027,863,  May  28,  1912;  727,650  and  728,173, 
May  12,  1903. 

t  British  Patent  26,928,  Nov.  27,  1906. 


212 


THE  HYDROGENATION   OF  OILS 


chiefly  carbon  dioxide,  with  but  little  carbon  monoxide  besides  hydro- 
gen, it  may  be  completely  liquefied,  and  the  hydrogen  recovered  by 
fractional  distillation.  In  either  case  the  hydrogen  resulting  is  further 
purified  by  being  conducted  over  calcium  carbide  at  a  temperature  of 
over  300°  C.* 

The  arrangement  of  a  plant  under  the  Linde-Frank-Caro  system  f 
is  shown  in  Fig.  64.     In  this  illustration  a  is  a  water-gas  generator  to 


FIG.  64. 


which  air  from  the  blower  b  and  steam  from  the  boiler  c  is  alternately 
supplied,  d  is  a  scrubber  and  e  a  gasometer.  1  is  a  water-gas  com- 
pressor, 2  an  air  compressor  and  3  a  refrigerating  apparatus.  Fore- 
coolers  for  drying  the  air  and  water  gas  are  shown  at  4.  A  water-gas 
separator  indicated  by  5  is  also  used  for  the  liquefaction  of  air.  A  gas 
engine  6  operated  by  the  rejected  carbon  monoxide  (collected  in  gasom- 
eter 7)  furnishes  power  for  running  the  compressors.  8  represents 

*  Frank  (J.  Gasbeleucht,  June  10,  1911)  has  recommended  (see  J.  S.  C.  I.,  1911, 
746)  that  apparatus  for  the  production  of  pure  hydrogen  and  other  gases  by  cooling 
and  liquefaction  should  be  installed  at  gas  works  making  water  gas  to  enable  hydro- 
gen to  be  supplied  on  the  large  scale. 

t  Gesellschaft  fur  Lindes  Eismas.chinen. 


LIQUEFACTION 


213 


FIG.  65.    Linde  hydrogen  apparatus. 

purifiers  for  removal  of  carbon  dioxide  *  and  9  soda-lime  purifiers  for 
the  ultimate  purification  of  the  hydrogen.  Before  purification  by 
soda  lime  the  gas  consists  of 

Per  cent 

Hydrogen  97-97.5 

Carbon  monoxide 1 . 7-2 

Nitrogen 1.0-1.8 

and  after  such  treatment  the  composition  is: 

Per  Cent 

Hydrogen 99.2-99.4 

Nitrogen f 0.6-  0.8 

An  apparatus  for  separating  hydrogen  from  the  other  constituents 
of  water  gas  is  shown  in  Fig.  66.  f 

*  The  Bedford  method  of  removing  carbon  dioxide  by  washing  the  gas  under 
high  pressure,  with  water,  is  used. 

t  Maschinenbau-Anstalt  Humboldt,  French  Patent  445,883,  July  8,  1912. 


214 


THE  HYDROGENATION  OF  OILS 


Water  gas  is  compressed  until  the  carbon  monoxide  is  liquefied,  impurities  such 
as  carbon  dioxide  are  removed  in  the  usual  manner,  and  the  mixture  of  hydrogen 
and  carbon  monoxide  is  introduced  into  a  separator  a,  from  which  it  passes  through 

a  concentric  tube  system  6,  in  counter- 
current  to  the  separated  cold  gases,  to  a 
worm  c,  situated  in  an  evaporator  d,  which 
is  partly  filled  with  liquid  carbon  monox- 
ide. The  mixture  expands  by  way  of  the 
valved  injector  e,  into  a  condenser  ht  at 
the  bottom  of  which  the  liquid  carbon 
monoxide  accumulates,  while  gaseous  hy- 
drogen ascends  into  a  riser  i.  Here  the 
entrained  carbon  monoxide  vapor  settles 
by  virtue  of  its  greater  density,  allowing 
pure  hydrogen  to  pass  by  way  of  an  over- 
flow-pipe k  into  the  concentric  tube  sys- 
tem b  and  out  of  the  separator  at  I.  The 
liquid  carbon  monoxide,  which  accumu- 
lates in  h,  passes  through  an  overflow-pipe 
m,  controlled  by  a  regulator  o,  down  along 
the  chamber  n,  into  the  evaporator  d, 
leaving  in  the  upper  part  of  n  any  ac- 
companying hydrogen,  which  may  be  with- 
drawn. The  liquid  carbon  monoxide, 
which  accumulates  at  the  bottom  of  d,  is 
evaporated  by  the  worm  c,  and  the  gaseous 
carbon  monoxide  escapes  by  way  of  the 
pipe  PJ  through  the  tubular  system  6,  and 
out  of  the  apparatus  at  I.  By  making  the  riser  i,  and  chamber  n,  of  the  requisite 
height,  the  two  gases  may  be  obtained  of  the  required  degree  of  purity. 

A  process  for  the  separation  of  hydrogen  from  carbon  dioxide  has 
been  proposed  by  Claude.*  The  hydrogen  containing  carbon  dioxide 
is  subjected  to  a  pressure  of,  say,  30  atmospheres,  and  is  then  passed 
through  heat-exchangers  wherein  it  meets  cold  gas  passing  in  an  oppo- 
site direction.  The  temperature  of  the  gaseous  mixture  falls  progres- 
sively, and  the  carbon  dioxide  gradually  liquefies.  The  temperature 
should  not  be  low  enough  for  the  production  of  solid  carbon  dioxide. 
The  counter-current  of  cold  gas  may  be  the  non-liquefied  portion  of  the 
compressed  gaseous  mixture,  the  cold  end  of  the  heat-exchanger  being 
cooled  externally  by  suitable  means.  Claude  f  partially  liquefies 
water  gas  or  analogous  gaseous  mixture  so  as  to  give  pure  hydrogen 
and  carbon  monoxide  containing  hydrogen  in  solution,  and  the  latter 
mixture  is  submitted  to  the  action  of  heated  slaked  lime  or  other 


FIG. 


*  French  Patent  375,991,  May  28,  1906. 
t  French  Patent  453,187,  March  28,  1912. 


LIQUEFACTION  215 

material  capable  of  reacting  to  yield  more  or  less  pure  hydrogen  which 
is  added  to  the  water  gas  about  to  be  treated.* 

Elworthy  f  separates  carbon  dioxide  from  a  mixture  of  gases  derived 
from  water  gas,  containing  hydrogen,  carbon  monoxide,  methane,  and 
carbon  dioxide  by  simple  compression  of  the  cooled  gaseous  mixture, 
or  by  compression  followed  by  expansion,  when  the  carbon  dioxide  is 
liquefied  or  solidified,  and  can  be  removed.  The  gases  escaping  from 
the  apparatus  are  utilized  for  cooling  the  incoming  gases. 

Jouve  and  Gautier  t  propose  to  pass  water  gas  through  a  porous 
partition,  such  as  unglazed  porcelain,  in  order  to  separate  hydrogen 
by  reason  of  its  rapid  power  of  diffusion.  It  is  said  that  by  one  such 
operation  the  percentage  of  carbon  monoxide  may  be  reduced  from 
45  to  8  per  cent. 

According  to  Elsworthy§  water  gas  may  be  passed  through  a  centrifugal  gaa 
separator,  which  is  said  to  remove  the  bulk  of  the  hydrogen,  almost  free  from 
other  gases. 

Separation  of  hydrogen  by  an  absorption  method  is  recommended 
by  Vignon.  ||  Water  gas,  cooled  and  washed,  is  treated  in  a  scrubber 
with  an  acid  or  alkaline  solution  of  cuprous  chloride,  thus  absorbing 
carbon  monoxide;  the  hydrogen  is  thereby  obtained  free  from  carbon 
monoxide.  The  latter  gas  is  recovered  by  heating  the  solution  or 
subjecting  it  to  reduced  pressure,  and  the  cuprous  chloride  is  then  used 
again.  The  carbon  monoxide  may  be  utilized  by  mixing  it  with  air 
and  burning  it  in  the  water-gas  generator,  so  as  to  supply  the  heat 
necessary  for  the  formation  of  the  water  gas,  or  this  may  be  effected 
by  burning  the  monoxide  in  a  vertical  shaft,  filled  with  refractory 
material,  fixed  in  the  center  of  the  generator. 

Frank  1f  passes  dry  water  gas  over  calcium  carbide  at  a  temperature 
above  300°  C.  Carbon  monoxide  reacts  with  the  carbide  forming 
calcium  oxide,  calcium  carbonate  and  carbon,  while  the  nitrogen 
present  is  converted  into  calcium  cyanamide.** 

*  The  Claude  Company  (Chem.  Ztg.  Rep.  (1913),  521;  French  Patent  453,187, 
March  28,  1912)  indicate  that  the  present  attainable  yield  (about  50  per  cent)  of  hy- 
drogen by  the  liquefaction  system  is  increased  and  the  loss  through  solution  of  hydro- 
gen in  carbon  monoxide  is  diminished  if  the  carbon  monoxide  gas  carrying  hydrogen 
is  subjected  to  the  action  of  hydrated  lime  to  form  calcium  carbonate  and  hydrogen 
and  the  impure  hydrogen  thus  secured  is  mixed  with  water  gas  and  further  treated 
in  a  similar  manner. 

t  First  Addition,  June  16,  1906,  to  French  Patent  355,324,  June  17,  1905. 

i  French  Patent  372,045,  1906. 

§  British  Patent  10,581,  May  5,  1906. 

II  French  Patent  389,671,  April  27,  1908. 

U  French  Patent  371,814,  1906. 
**  Thorpe  Diet.  App.  Chem.  III.,  61. 


216  THE  HYDROGENATION  OF  OILS 

Frank  conducts  water  gas  through  milk  of  lime  to  remove  carbon 
dioxide,  then  through  cuprous  chloride  in  hydrochloric  acid  solution 
to  remove  carbon  monoxide  and  over  heated  calcium  carbide  to  re- 
move nitrogen  as  cyanamide.  The  carbide  also  removes  traces  of 
carbon  monoxide  and  dioxide  with  separation  of  carbon  in  a  finely- 
divided  condition.  The  cuprous  chloride  solution  is  regenerated  by 
exposing  to  reduced  pressure  to  remove  the  monoxide.*  Subsequently 
Frank  stated  f  that  the  expense  of  carbide,  or  of  cuprous  compounds 
or  other  means  of  absorbing  carbon  monoxide,  was  found  to  be  too 
great  and  ultimately  he  was  led  to  adopt  the  method  of  removal  by 
liquefaction.! 

*  Chemie  der  Case,  Brahmer  (1911),  97. 

t  J.  S.C.I.,  1911,746. 

J  See  also  Frank,  U.  S.  Patent  873,853,  Dec.  17,  1907. 


CHAPTER  XV 
HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS 

When  methane  is  heated  to  1200°  to  1300°  C.  dissociation  occurs 
and  lamp-black  and  hydrogen  are  produced.  Acetylene  is  decom- 
posed at  a  much  lower  temperature.  In  general,  when  subjected  to 
sufficient  heat  hydrocarbons  break  down  into  their  elements.  This 
fact  has  been  made  use  of  for  the  production  of  hydrogen  by  decom- 
posing various  hydrocarbons  and  particularly  heavy  oils.  Among  the 
proposals  put  forward  up  to  the  present  time  are  some  which  relate  to 
the  splitting  of  acetylene  or  natural  gas  by  passage  through  the  heat 
zone  of  an  electric  arc  and  separation  of  the  hydrogen  from  the  lamp- 
black or  other  carbonaceous  material  which  is  formed.  The  gas  may 
be  under  pressure  to  render  the  decomposition  more  effective. 

Pictet  accomplishes  this  decomposition  by  treatment  of  the  gas  in 
heated  tubes,*  as,  for  instance,  an  endothermic  hydrocarbon,  such  as 
acetylene,  is  passed  through  a  tube,  the  front  portion  of  which  is 
heated  to  about  500°  C.,  at  which  temperature  the  gas  dissociates  into 
its  elements  with  the  evolution  of  a  large  quantity  of  heat.  The  latter 
raises  the  temperature  of  the  tube  sufficiently  to  dissociate  fresh 
quantities  of  acetylene  without  the  further  application  of  external 
heat.  The  rear  portion  of  the  tube  is  surrounded  by  a  refrigerating 
appliance,  and  the  products  of  decomposition,  hydrogen  and  lamp- 
black, are  passed  into  a  suitable  apparatus  for  their  separation.  In 
the  same  way  exothermic  hydrocarbons,  such  as  petroleum  vapors, 
mixed  with  steam  may  be  decomposed  with  the  formation  of  hydrogen 
and  carbon  monoxide;  in  this  case  the  combination  of  nascent  carbon 
and  oxygen  supplies  a  portion  of  the  heat  required  by  the  reaction, 
the  balance  which  is  required  to  dissociate  steam  and  hydrocarbon 
being  supplied  by  external  heating.  By  admitting  a  regulated  quan- 
tity of  oxygen,  the  combination  of  the  latter  with  nascent  carbon  may 
be  made  to  provide  all  the  heat  required  by  the  reaction,  it  being  then 
only  necessary  to  heat  the  hydrocarbons  initially  to  their  temperature 
of  dissociation.  The  apparatus  may  conveniently  consist  of  a  steel, 
iron  or  porcelain  tube,  one  portion  of  which  is  heated  by  means  of  a  gas 
furnace,  and  the  other  cooled  by  water,  or  by  a  liquid  hydrocarbon, 

*  French  Patent  421,838,  Oct.  26,  1910. 
217 


218 


THE  HYDROGENATION  OF  OILS 


the  vapors  of  which  are  afterwards  admitted  to  the  tube  for  their  dis- 
sociation. The  tube  is  provided  with  the  conduits  necessary  for  the 
admission  of  the  raw  materials  and  for  the  withdrawal  of  the  products 
of  dissociation,  these  conduits  being  preferably  composed  of  "  pure 
iron  "  covered  with  nickel;  the  lamp-black  is  separated  by  washing 
or  by  means  of  niters. 

In  a  modification  of  the  foregoing  Pictet  (British  Patent  14,703,  June  21,  1911) 
operates  in  such  a  way  that  the  carbon,  instead  of  being  deposited  in  the  form  of 
soot,  is  converted  into  carbon  monoxide  by  interaction  with  water  vapor.  External 

heat  (39.36  units  for  every  18  grams  of 
water)  is  applied  for  decomposing  the 
water  vapor,  in  addition  to  that  required 
to  decompose  the  hydrocarbon  vapors, 
for  which  the  temperature  is  raised  sub- 
stantially to  the  melting  point  of  iron. 
Water  and  hydrocarbon  are  fed,  for  ex- 
ample, into  an  iron  tube,  which  is  of 
sufficient  length  (say  3  to  4  meters)  to 
enable  the  supplementary  heat  to  be 
imparted  without  damage,  and  these 
being  vaporized  on  entry,  react  in  the 
further  end  of  the  tube,  which  is  the 
more  strongly  heated;  the  gas  produced 
is  then  cooled  and  passes  through  a  filter 
to  a  gas  holder,  there  being  a  soot 
chamber  and  also  arrangements  for  the 
removal  of  soot  from  the  tube  and  filter. 
Ten  liters  of  petroleum,  mixed  with  3  to 
5.5  liters  of  water,  may  be  thus  decom- 
posed per  hour,  in  the  apparatus  de- 
scribed, the  mixture  furnishing  approx- 
imately 3000  liters  of  gas  for  every  liter 
of  hydrocarbon,  with  a  calorific  value  of 
3000  to  3600  heat  units  per  cubic  meter. 
By  regulating  the  supply  of  water,  any 
FIG.  67.  desired  proportion  of  carbon  can  be  con- 

verted into  carbon  monoxide. 

In  preparing  hydrogen  from  crude  petroleum  or  petroleum  tar  oils  (British  Patent 
13,397,  June  3,  1911)  the  vapors  are  heated  in  such  a  manner  that  18.1  calories  are 
supplied  to  16  grams  of  gas,  with  a  tube  temperature  of  1200°  to  1350°  C. 

Another  process  worked  out  by  the  Carbonium  Company  in  Germany 
employs  acetylene  gas  which  is  compressed  to  two  atmospheres  and 
exploded  by  an  electric  spark.* 

C2H2   =    C2  ~}~  H-2. 

The  acetylene  thereby  dissociates  into  the  elements  carbon  and  hydro- 
*  Met.  and  Chem.  Eng.  (1911),  157. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS      219 

gen.  The  carbon  deposits  in  the  form  of  lamp-black.  The  hydrogen 
is  passed  through  large  washer  and  stored.  Its  degree  of  purity  is  ex- 
ceptionally high.  For  each  cubic  meter  of  hydrogen  produced  about 
one  kilo  of  lamp-black  is  formed.  A  condition  for  getting  the  hydrogen 
cheaply  by  this  method  is  that  there  is  a  market  for  the  lamp-black. 

Wachtolf  *  compresses  the  acetylene  to  about  4  to  6  atmospheres 
and  explodes  electrically.  In  Fig.  67  the  explosion  chamber  is  shown 
on  the  left  and  a  lamp-black  collector  on  the  right.  The  explosion 
chamber  is  provided  with  a  rotary  scraper  to  remove  lamp-black 
adhering  to  the  walls,  f 

Geisenberger  {  generates  hydrogen  alone  or  mixed  with  carbon 
monoxide  or  carbon  dioxide,  by  the  action  of  heat  alone  or  of  heat  and 
steam,  on  light  hydrocarbons,  such  as  benzine,  or  on  other  materials 
containing  hydrogen  and  carbon,  e.g.,  bitumen,  shale,  beeswax,  tur- 
pentine, etc.  The  organic  substance  is  heated  in  a  retort,  to  which 
steam  may  be  admitted,  to  its  point  of  decomposition.  The  hydro- 
gen is  separated  from  the  other  gases  in  the  mixture  obtained,  either 
by  physical  means,  depending  on  the  differences  in  density,  or  by 
chemical  means,  such  as  absorbing  the  carbon  dioxide  by  means  of 
sodium  carbonate  or  hydroxide  solution. 

Rincker  and  Wolter  §  make  use  of  two  generators,  somewhat  re- 
sembling those  used  in  making  water  gas,  for  the  decomposition  of 
oils  and  tars.  These  generators  are  arranged  side  by  side  and  charged 
with  coke.  After  they  have  been  raised  to  incandescence  by  a  blast 
of  air,  a  charge  of  tar  is  introduced  into  one  of  them  and  is  partly 
transformed  into  gas  by  the  glowing  fuel.  The  gas  formed  escapes 
by  its  own  expansion.  A  current  of  air  is  then  introduced  which 
carries  forward  the  remaining  vapors  of  tar  into  the  second  generator 
where  they  are  converted  into  a  permanent  gas.  At  the  same  time 
the  blast  of  air  raises  the  contents  of  the  fir^te^^rator  to  incandescence 
again,  and  the  process  is  reversed  by*j^H  i^g  the  tar  into  the 
second  generator  and  repeating  the  ope^^^^^^fce  reverse  direction. 

In  a  modified  form  of  the  apparatus  ||  the  two  ucnenitors  are  ar- 
ranged one  above  the  other  and  are  r harmed  with  coke.  The  coke  in 
the  lower  generator  is  ignited  and  then  brought  to  incandescence  by 
a  blast  of  air  which  has  been  preheated  by  beinj^msed  to  pass  through 
a  jacket  surrounding  the  upper  generator.  The  fuel  in  the  latter  is 

*  German  Patent  194,301. 

f  Decomposition  of  hydrocarbons  under  pressure  is  described  by  Bosch,  German 
Patent  268,291,  July  14,  1911;  Chem.  Zeit.  Rep.  (1914),  32. 
t  French  Patent  361,492,  Dec.  21,  1905. 
§  French  Patent  391,868,  May  11,  1908. 
i|  French  Patent  391,867,  May  11,  1908. 


220 


THE  HYDROGENATION  OF  OILS 


also  ignited  and  then  raised  to  incandescence  by  natural  draught. 
The  products  of  combustion  are  allowed  to  escape  to  the  chimney. 
When  the  fuel  is  glowing  brightly,  the  air  supply  is  cut  off  and  a  charge 
of  oil  is  introduced  into  the  lower  generator  through  pipes  in  the  top. 
The  oil  passes  over  the  glowing  fuel  and  is  partially  converted  into 
permanent  gas  which  escapes  through  a  pipe  in  the  side  by  its  own 


FIG.  68. 

expansion.  The  blast  of  air  is  then  again  turned  on,  whereby  the 
vapors  of  oil  left  in  the  lower  generator  are  blown  into  the  upper  one, 
where  they  are  gasified  and  fixed  during  their  passage  through  the 
glowing  fuel.  The  lower  generator  is  at  the  same  time  again  raised  to 
incandescence  and  the  process  is  repeated.* 

*  Apparatus  for  the  production  of  hydrogen  by  the  decomposition  of  the  vapors 
of  oil  or  tar  by  exposure  to  a  high  temperature  is  the  basis  of  a  patent  to  the  Berlin- 
Anhaltische  Maschinenbau-Aktien-Gesellschaft,  Berlin,  German  Patent  267,944, 
Jan.  28,  1913;  Chem.  Zeit.  Rep.  (1914),  31. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS      221 

Equipment  for  the  Rincker-Wolter  system  is  manufactured  by  the  Hollandsche 
Residugas-Maatschappij  of  Rotterdam.  The  gas-making  plant  consists  of  twin 
generators,  Fig.  68,  lined  with  firebrick  and  provided  with  grate  bars  and  clinkering 
doors,  in  short,  resembling  water-gas  generators  but  lacking  a  carburettor  and  super- 
heater. The  generators  are  connected  near  the  top  and  in  the  upper  part  are  lids 
for  feeding  purposes,  which  carry  sprayers  for  introduction  of  the  oil. 

Fig.  69  shows  the  operating  floor  of  one  of  these  plants.     The  generators  are 


FIG.  69. 

equipped  with  primary  and  secondary  blast  pipes,  steam  inlets  and  dust  collectors. 
Both  generators  are  charged  with  coke  and  fired.  The  generators  are  operated 
alternately  in  the  blowing-run,  the  first  generator  receiving  the  primary,  and  the 
second  generator  the  secondary,  air  blast.  Combustion  is  incomplete  in  the  first 
generator  and  the  producer  gas  obtained  is  led  to  the  second  generator  where  it  is 
burned  on  meeting  the  current  of  secondary  air,  thus  heating  up  the  second  generator. 
As  it  is  preferable  to  reach  nearly  equal  temperatures  in  both  generators,  the 
sequence  is  reversed  after  a  short  blowing  and  the  first  generator  becomes  second  in 
the  series.  When  both  generators  have  reached  the  proper  temperature,  the  air 
valves  are  shut  and  the  gas  run  begins.  The  temperature  of  the  fuel  bed  has  to 
be  varied  somewhat  according  to  the  nature  of  the  raw  materials.  For  hydrogen 
production  a  temperature  of  about  1200°  C.  is  required.  Too  low  a  temperature 
gives  so  impure  a  gas  that  subsequent  purification  of  the  hydrogen  is  rendered  costly. 
At  the  end  of  the  blowing-run  oil  is  sprayed  for  several  minutes  on  the  hot  coke  and 
gasification  takes  place.  Immediately  after  this  the  sprayer  is  cleaned  by  blowing 
steam  through  it.  The  gas  formed  by  decomposition  of  the  oil  passes  to  a  seal  and 
from  there  to  scrubbers  and  purifiers. 


222  THE  HYDROGENATION  OF  OILS 

Fig.  70  shows  the  gas  outlets  and  seal.  The  residue  of  gas  in  the 
generators  is  expelled  by  steam.  Lamp-black  is  deposited  in  the 
generators  and  is  consumed  in  the  next  run.  Fig.  71  shows  the  gener- 
ators of  a  plant  at  Utrecht. 

In  a  well-handled  run  gas  of  the  following  composition  is  said  to  be 
obtained : 

Per  cent 
H 96 

N 1.3 

CO v       2.7 

And  by  passing  this  gas  over  heated  soda-lime  a  gas  has  been  secured 
analyzing: 

Per  cent 

H 98.4 

N 1.2 

CO* 0.4 

To  avoid  difficulties  from  clinkering  of  the  ash  of  the  fuel,  the  author 
has  suggested  the  addition  of  a  small  proportion  of  lime  to  the  charge  of 
coke,  so  as  to  flux  the  ash  and  thus  to  enable  the  maintenance  of  the 
requisite  high  temperature  in  the  fuel  bed.f 

A  method  of  preparing  hydrogen  is  proposed  by  the  Badische  Anilin 
und  Soda  Fabrik  {  according  to  which  a  mixture  of  hydrocarbons  and 
steam  is  passed  over  an  inactive,  refractory  oxide,  such  as  magnesia, 
coated  with  nickel  or  nickel  oxide,  at  a  temperature  of  800°  to  1000°. 
The  resulting  gaseous  mixture  is  freed  from  carbon  monoxide  and 
dioxide,  leaving  substantially  pure  hydrogen. 

Efforts  to  secure  hydrogen  from  illuminating  gas  have  met  with  a 
considerable  measure  of  success.  By  the  process  of  Oechelhauser 
hydrogen  of  about  80  per  cent  purity  is  obtained.  A  gas  of  much 
higher  hydrogen  content  has  been  produced  by  the  Berlin-Anhaltischen 
Maschinenbau  —  A.—  G.  which  is  based  on  investigations  made  by 
Bunte.  The  illuminating  gas  is  first  freed  of  carbon  dioxide  and  is 
then  conducted  over  white-hot  coke  which  decomposes  the  hydro- 
carbons and  yields  a  gas  mixture  consisting  almost  entirely  of  hydro- 
gen, carbon  monoxide  and  nitrogen.  The  carbon  monoxide  is  removed 

*  Sanders  (Zeitsch.f.angew.  Chem.  (1912),  2404)  states  that  the  cost  of  hydrogen 
by  the  Rincker-Wolter  system  is  10.5  to  14  pfennig  per  cubic  meter.  In  a  private 
communication  to  the  author,  the  manufacturers  advise  the  cost  of  the  smallest 
equipment  they  make,  having  a  capacity  of  3500  cubic  feet  of  hydrogen  per  hour,  is 
$2575  plus  erecting  expenses.  With  oil  at  about  4  cents  per  gallon  the  hydrogen  is 
estimated  to  cost  about  $1.75  per  thousand  cubic  feet. 

t  Ellis,  U.  S.  Patent,  1,092,903,  April  14,  1914. 

J  J.  S.  C.  I.,  1914,  313. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS      223 


FIG.  70. 


Fia.  71. 


224  THE  HYDROGENATION  OF  OILS 

by  treatment  with  soda  lime  and  the  gas  then  consists  largely  of  hydro- 
gen with  only  nitrogen  as  an  impurity.  The  specific  gravity  is  0.085 
to  0.097  and  the  gas  has  been  found  to  be  well  adapted  for  most 
technical  purposes.  The  process  can  be  put  in  operation  at  any  gas 
works  equipped  with  a  water-gas  plant  and  the  installation  is  not 
very  costly.* 

*  Sander  Zeitsch.  f .  angew.  Chemie  (1912),  2406. 


CHAPTER  XVI 

HYDROGEN  BY  THE  ACTION   OF   STEAM   ON   HEATED 

METALS 

A  large  number  of  proposals  for  making  hydrogen  exist  which  are 
based  on  a  very  old  reaction,  namely,  the  passage  of  steam  over  red 
hot  iron  in  a  finely-divided  state.     The  main  reaction  which  occurs  is 
3  Fe  +  4  H2O  =  Fe304  +  4  H2. 

On  the  large  scale  it  becomes  necessary  to  regenerate  the  iron  material ; 
which  is  effected  by  reduction,  usually  with  water  gas.  With  an  im- 
pure gas  slagging  difficulties  arise.  Giffard  found  that  the  charge  of 
iron  soon  became  inefficient  because  the  sulfur  in  the  gas  formed  on 
the  iron  particles  a  resistant  coating  of  iron  sulfide,  which  also  acted 
as  a  flux  and  caused  the  iron  material  to  sinter  into  a  coherent  mass. 
Hence  prior  purification  of  the  reducing  gas  was  found  necessary  for 
satisfactory  operation.  Apart  from  the  sintering  effect  of  sulfur  on 
the  iron  material,  the  water  gas  should  be  freed  from  this  element  as 
otherwise  the  hydrogen  would  take  up  sulfur  and  poison  the  cata- 
lyzer. For  each  cubic  foot  of  hydrogen  produced,  about  three  cubic 
feet  of  water  gas  are  required.  This  requires  the  purification  of  three 
volumes  of  water  gas  for  one  volume  of  hydrogen. 

Some  of  the  processes  described  have  had  little  or  no  commercial 
success,  but  are  included  because  they  involve  certain  features  which 
are  suggestive  or  instructive. 

Lewes  *  prepared  hydrogen  in  the  following  manner: 

A  retort,  partly  filled  with  iron  borings,  or  with  a  mixture  of  iron  and  carbonaceous 
material,  or  with  asbestos  containing  iron  in  a  very  fine  state  of  division,  is  placed 
in  the  center  of  a  gas  producer.  By  means  of  an  air  blast  the  fuel  in  the  producer 
is  raised  to  a  bright  red  heat  and  then  a  little  steam  is  admitted  together  with  the 
air.  The  gaseous  mixture  of  carbonic  oxide,  nitrogen  and  hydrogen  produced  in 
this  way  is  led  from  the  top  of  the  producer  down  through  the  retort.  As  soon  as 
the  iron  oxide  in  the  retort  is  completely  reduced,  and  the  requisite  temperature 
has  been  attained,  the  producer  gas  is  turned  off  and  steam,  previously  heated  in 
the  producer,  is  passed  over  the  iron,  the  hydrogen  being  led  away  to  a  gasometer. 
The  process  is  then  repeated  as  described.  One  of  the  advantages  claimed  for 
this  form  of  apparatus  is  that  the  rapid  cooling  of  the  iron  during  the  decomposition 
of  the  steam  is  prevented.  Lewes  claims  (British  Patent  4134,  March  7,  1891)  the 

*  British  Patent  20,752,  Dec.  19,  1890. 
225 


226  THE  HYDROGENATION  OF  OILS 

use  of  a  mixture  of  carbonic  oxide,  nitrogen  and  hydrogen  for  the  reduction  of  oxide 
of  iron  in  the  above  process.  This  gaseous  mixture  is  regarded  as  a  better  reducing 
agent  than  carbonic  oxide,  and  is  easily  obtained.  The  finely-divided  iron  employed 
for  the  production  of  hydrogen  is  prepared  by  saturating  asbestos  or  pumice  with 
certain  iron  salts,  which  are  easily  decomposed  into  oxide  of  iron  on  heating,  or  by 
mixing  moist  hydrated  oxide  of  iron  with  asbestos  fiber  and  iron  filings. 

The  Dellwik-Fleischer  Wassergas-Ges.  m.  b.  H.*  prepare  iron  by 
the  reduction  of  a  mineral  oxide  which  retains  both  porosity  and  re- 
sistance after  repeated  use.  In  order  to  prevent  deposition  of  carbon 
during  the  reduction  of  the  iron  oxide  in  the  retort,  the  reducing  gas 
is  mixed  with  a  volume  of  steam  equal  to  at  least  half  the  sum  of  the 
carbon  monoxide  and  hydrocarbons  present  in  it.  It  is  also  found 
economical  to  carry  the  reduction  only  half  way  instead  of  completely 
to  the  metal,  and  this,  moreover,  gives  purer  hydrogen  since  no  carbon 
can  be  deposited  during  such  partial  reduction.  In  British  Patent 
7849,  of  1909,  the  Dellwik-Fleischer  Co.  make  use  of  iron  pyrites 
roasted  to  expel  all  sulfur  and  volatile  metals. f 

Hydrogen  gas  is  produced  according  to  Hills  and  Lane  J  by  passing 
steam,  preferably  superheated,  over  iron  contained  in  heated  retorts; 
and  the  mixture  of  hydrogen  and  steam  is  led  through  coolers,  from 
which  the  hydrogen  passes  to  a  gasometer.  By  means  of  reversing 
valves,  controlling  inlet  and  outlet  passages,  a  reducing  gas,  such  as 
water  gas,  coal  gas  or  the  like,  is  then  led  through  the  retorts  to  reduce 
the  iron  oxide  formed,  and  then  steam  is  again  passed  through.  Lane 
and  Monteux  §  secure  the  production  of  pure  or  nearly  pure  hydrogen 
in  a  continuous  manner  by  the  action  of  steam  on  red-hot  iron.  Finely- 
divided  iron  is  contained  in  a  series  of  vertical  retorts,  heated  exter- 
nally by  gas,  in  combination  with  a  regenerative  system.  The  retorts 
are  so  connected  that  a  current  of  steam  passes  through  some,  while 
the  iron  oxide,  already  formed,  is  being  reduced  in  others  by  a  stream 
of  reducing  gas  sent  in  the  opposite  direction.  Oxidation  and  reduc- 
tion thus  take  place  alternately,  oxidation  being  found  to  occupy  only 
half  the  time  of  reduction.  The  hydrogen  produced  is  cooled  and 
purified,  to  remove  traces  of  carbon  dioxide,  etc.  The  reducing  gas 
is  made  in  a  producer,  and  by  introducing  an  excess  of  steam,  it  be- 
comes rich  in  hydrogen.  The  excess  of  reducing  gas  is  utilized  for 
heating  the  retorts.  After  repeated  use  the  iron  becomes  inactive, 
owing  to  an  accumulation  of  impurities,  but  if  these  are  burned  away 

*  French  Patent  395,132,  Oct.  10,  1908. 

t  British  Patent  21,479,  Oct.  10,  1908,  and  7849,  April  1,  1909. 

t  British  Patent  10,356,  May  7,  1903. 

§  French  Patent  386,991,  Feb.  7,  1908. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      227 

by  the  occasional  admission  of  air,  the  efficiency  of  the  iron  is  said  to 
be  restored. 

As  it  has  been  found  in  practice  that  the  reducing  reaction  takes  considerably 
longer  than  the  generation  of  hydrogen,  the  Lane  process  (British  Patent  17,591, 
July  29,  1909)  may  be  carried  out  in  three  or  more  groups  of  retorts,  the  greater  part 
of  which  are  constantly  subjected  to  the  action  of  reducing  gases  for  the  regeneration 
of  the  iron,  or  other  hydrogen-producing  substance.  The  retorts  communicate 
with  one  another  by  means  of  a  series  of  pipes,  fitted  with  controlling  valves,  so 
that  steam  or  the  reducing  gases  may  be  admitted  as  required.  The  hydrogen, 
which  is  evolved  in  the  first  few  minutes  of  the  operation,  being  impure,  is  diverted 
from  the  collector  of  pure  hydrogen,  and  mixed  with  the  water  gas  used  for  reduction. 
A  considerable  excess  of  water  gas  is  used  for  reduction,  and  it  undergoes  a  very 
thorough  system  of  purification  before  being  admitted  to  the  retorts;  the  excess, 
which  issues,  is  freed  from  the  accompanying  steam  and  used  again.  Means  are 
provided  for  forcing  hot  air  through  the  reaction  chamber,  which  is  done  periodically 
between  the  two  reactions  so  as  to  burn  out  objectionable  impurities,  especially 
sulfur.  For  the  purification  of  the  excess  of  water  gas,  or  other  reducing  medium, 
which  issues  unchanged  from  the  reducing  retorts,  the  gas  is  passed  into  a  cooler 
and  washer,  which  removes  mechanical  impurities,  and  thence  into  a  compressor. 
From  the  latter  it  passes  under  a  pressure  of  several  atmospheres  into  a  strong 
receiver.  The  latter  contains  coke  or  the  like  material,  down  which  cold  water  is 
distributed  by  means  of  a  pump  or  other  forcing  device.  The  compressed  gas, 
coming  into  contact  with  cold  water,  is  freed  from  such  impurities  as  sulfur  dioxide, 
hydrogen  sulfide,  carbon  dioxide,  etc.,  either  by  solution  or  by  condensation,  being 
at  the  same  time  deprived  of  the  greater  part  of  its  moisture.* 

With  the  Lane  and  -similar  apparatus  it  has  been  found  f  that  the 
hydrogen  gas  obtained  contains  a  relatively  large  proportion  of  gaseous 
and  solid  bodies  or  impurities,  produced  concurrently  with  the  hydro- 
gen and  whose  presence  considerably  increases  the  quantity  of  reducing 
gas  necessary  for  carrying  out  the  reduction  operation,  as  well  as  the 
time  necessary  for  effecting  the  deoxidation  of  the  contact  material. 
The  presence  of  these  impurities  in  the  hydrogen  gas  is  due  to  the  fact 
that  the  reducing  agent  contains  sulfur,  carbon,  etc.,  which  either 
become  deposited  on  the  contact  material  or  generate  gases  such  as 
sulfurous  acid,  sulfuretted  hydrogen  or  carbon  dioxide.  After  the 
reduction  phase  a  certain  quantity  of  free  reducing  gas  still  remains 
in  the  retort,  the  presence  of  which  contaminates  the  hydrogen  and 
consequently  lessens  its  commercial  value. 

Lane,  therefore,  proposes  means  for  removing  the  reducing  gas  as 
well  as  the  sulfur,  carbon  and  other  impurities  between  the  two 
oxidizing  and  reducing  steps  of  the  process.  To  this  end  the  retort 
is  provided  at  each  extremity  with  a  multiple-way  controlling  valve 
adapted  to  establish  communication  between  that  end  of  the  retort 

*  Lane,  British  Patent  11,878,  Jan.  29,  1910. 
t  Lane,  U.  S.  Patent  1,028,366,  June  4,  1912. 


228 


THE  HYDROGENATION  OF  OILS 


and  any  one  of  three  pipes  connected  respectively  at  the  one  end  of  the 
retort  to  a  supply  of  air  under  pressure,  a  supply  of  reducing  gas,  and 
a  hydrogen  receiver,  and  at  the  opposite  end  of  the  retort  respectively 
to  an  outlet,  a  gas-washing  and  regenerating  apparatus,  and  a  supply 
of  steam  under  pressure. 

In  Fig.  72  A  is  the  retort  provided  with  an  inlet  B  at  the  lower  end  and  an  outlet 
C  at  the  upper  end,  and  F  and  G  are  four-way  valves  which  are  capable  of  being 
rotated  by  means  of  hand-wheels  H  and  J  so  as  to  open  communication  on  the  one 
hand  between  the  retort  A  and  either  the  pipe  K  connected 
to  a  hydrogen  container,  a  pipe  M  connected  to  a  supply 
of  reducing  gas,  or  a  pipe  N  connected  to  a  supply  of  air 
under  pressure,,  and  on  the  other  hand  either  with  a  dis- 
charge pipe  0,  a  pipe  P  leading  to  a  gas-washing  or  regen- 
erating apparatus  and  a  pipe  Q  connected  to  a  supply  of 
low-pressure  steam.  Assuming  that  the  contact  material 
in  the  retort  has  been  oxidized  during  the  previous  hydro- 
gen-producing phase,  the  sequence  of  operations  is  as 
follows.  In  the  first  place  the  impurities  deposited  on  the 
contact  material  during  the  previous  reduction  phase,  or 
present  in  the  gaseous  state  in  the  retort,  are  removed  by 
effecting  their  combustion.  This  is  effected  by  rotating 
the  valve  G  one-quarter  of  a  revolution  so  as  to  admit 
air  under  pressure  to  the  lower  part  of  the  retort  through 
the  pipes  N  and  D,  and  rotating  valve  F  so  as  to  force 
out  the  products  of  combustion  into  the  atmosphere 
through  the  pipes  E  and  0.  The  valve  G  is  then  rotated 
S3  as  to  admit  reducing  gas  to  the  retort  through  pipes 
M  and  D  and  rotating  valve  F  so  as  to  open  communi- 
cation between  the  upper  part  of  the  retort  and  the  gas- 
washing  or  regenerating  apparatus  through  pipes  E  and  P. 
At  the  completion  of  the  reducing  phase  the  valve  F  is 
rotated  so  as  to  connect  the  upper  part  of  the  retort  with 
the  supply  of  steam  under  pressure  through  pipes  Q  and 
E,  whereupon  the  pressure  of  the  steam  being  greater 
than  that  of  the  reducing  gas  remaining  in  the  retort,  the  latter  is  forced  out 
through  pipes  D  and  M  carrying  with  it  the  impure  hydrogen  which  has  been 
generated  by  the  action  of  the  steam  on  the  sulfur,  carbon,  etc.,  deposited  on  the 
contact  material.  As  soon  as  it  is  found  that  the  hydrogen  passing  out  through 
pipe  M  is  sufficiently  pure  the  valve  G  is  rotated  so  as  to  deliver  the  gas  to  the 
hydrogen  container,  after  which,  air  is  then  again  passed  through  the  retort  in  the 
manner  previously  described.* 

*  Lane  (U.  S.  Patent  1,040,218,  Oct.  1,  1912)  purifies  the  reducing  gas  in  the 
manufacture  of  hydrogen  by  the  alternate  oxidation  and  deoxidation  of  iron,  by 
compressing  the  reducing  gas  to  a  pressure  of  several  atmospheres  and  then  causing 
it  to  flow  (while  still  under  pressure)  in  contact  with  an  oppositely  flowing  stream 
of  water.  To  increase  the  effectiveness  of  the  washing  operation,  the  gas  is  passed 
through  a  coke  tower  through  which  water  is  flowing  in  an  opposite  direction. 


FIG.  72. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      229 

Fig.  73  shows  the  Lane  system  as  installed  in  the  works  of  a  large 
soap  manufacturer  in  England.  Figs.  74  and  75  show  the  same  system 
installed  at  a  plant  near  Paris. 

Lane  states  *  that  in  practice  it  has  been  found  difficult  to  obtain 
pure  hydrogen  in  consequence  of  the  steam  admitted  to  the  retort 
during  the  oxidation  state  coming  into  contact  with  the  reducing  gas 
admitted  during  the  previous  reduction  state  and  with  the  sulfur, 
carbon,  etc.,  associated  with  and  introduced  into  the  retort  by  this 


L 


gas,  the  result  of  which  contact  being  the  formation  of  sulfuretted 
hydrogen,  sulfurous  acid,  carbon  dioxide,  etc.,  and  consequent  con- 
tamination of  hydrogen  produced  by  the  action  of  the  steam.  Lane 
proposes  to  remove  the  sulfur,  carbon  and  other  impurities  left  by  the 
reduction  phase,  by  admitting  air  under  pressure  to  the  retort  and 
discharging  the  products  of  combustion  into  the  atmosphere.  The 
admission  of  air  to  the  retort  and  the  discharge  of  the  products  of 
combustion  then  ceases  and  reducing  gas  is  admitted  and  passed 
through  and  out  of  the  retort  to  a  gas-washing  and  regenerating  appara- 
tus. When  the  reduction  stage  has  been  completed  the  admission  of 
reducing  gas  is  shut  off  and  steam  admitted.  As  a  certain  proportion 
of  reducing  gas  will  then  be  present,  impure  hydrogen  will  be  produced 
and  this  is  allowed  to  go  to  waste,  until  the  product  is  found  to  be 
sufficiently  pure.  Thereupon  the  outlet  to  the  atmosphere  is  closed 
and  the  hydrogen  passed  into  a  storage  tank. 

*  U.  S.  Patent  1,078,686,  Nov.  18,  1913. 


230 


THE  HYDROGENATION  OF  OILS 


A  process  devised  by  Messerschmitt  *  depends  upon  the  alternate 
oxidation  of  spongy  iron  by  means  of  steam,  with  the  evolution  of 


FIG.  74. 


hydrogen,  and  the  reduction  of  the  resulting  iron  oxide  f  by  means  of 
reducing  gases,  such  as  water  gas. 


FIG.  75. 

*  French  Patent  444,105,  May  22,  1912. 

t  After  iron  oxide  has  been  used  for  a  time  it  becomes  partially  or  wholly  inac- 
tive and  has  to  be  replaced  by  fresh  material.  It  has  been  proposed  to  make  the 
reducing  chamber  vertical  with  a  grate  at  the  bottom  through  which  the  spent  oxide 
may  be  removed  from  time  to  time  just  as  ashes  are  withdrawn  from  a  gas  producer. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS     231 

An  upright,  cylindrical  reaction  chamber  made  of  iron  is  suspended  inside  a 
furnace  chamber,  with  which  it  is  in  open  communication  at  the  bottom,  the  lower 
end  of  the  cylinder  being  provided  with  a  grate  to  support  the  column  of  reacting 
material.  The  width  of  the  reaction  cylinder  is  relatively  small,  so  that  the  contents 
may  readily  be  heated  from  all  sides,  and  the  furnace  chamber  is  provided  with 
checkerwork  constituting  a  superheater.  Both  the  reaction  cylinder  and  the 
furnace  chamber  are  capable  of  being  sealed,  and  are  provided  with  a  system  of 
pipes  and  valves,  enabling  the  introduction  of  either  steam  or  water  gas  into  the 
reaction  cylinder  or  the  furnace  chamber.  An  air-supply  pipe  communicates  with 
the  furnace  chamber,  and  a  pipe  leading  from  the  top  of  the  reaction  cylinder  can 
be  put  into  communication  with  a  gas  purifier  and  the  steam-raising  plant.  The 
process  is  carried  out  in  three  phases ;  water  gas  and  air  are  first  burned  in  the  furnace 
chamber  until  the  material  inside  the  reaction  cylinder  has  reached  the  required 
temperature.  The  air  supply  is  then  cut  off  and  water  gas,  flowing  in  at  the  bottom 
of  the  furnace,  becomes  strongly  heated,  enters  the  open  lower  end  of  the  cylinder, 
traverses  the  mass  of  iron  oxide  in  an  upward  direction,  and  finally  passes  off  at 
the  top  to  the  steam-raising  plant,  where  any  combustible  gases  are  utilized.  When 
the  reduction  of  the  iron  oxide  is  complete  the  supply  of  water  gas  is  cut  off  and 
steam  is  introduced,  first  into  the  bottom  of  the  furnace  to  sweep  out  any  residual 
gases  from  the  second  operation  (the  furnace  being  in  direct  communication  with 
the  chimney  while  this  is  going  on),  and  then  into  the  top  of  the  furnace  chamber, 
from  which  it  passes  downwards  through  the  hot  checker-work  and  finally  upwards 
through  the  mass  of  spongy  iron.  Hydrogen  issues  from  the  top  of  the  reaction 
cylinder  and  travels  through  a  purifier  into  a  gasometer.  The  iron  receptacle  may 
take  the  form  of  two  concentric  cylinders,  the  reaction  material  being  in  that  case 
charged  into  the  annular  space  between  the  two.  The  cylinders  are  periodically 
heated  and  reduced  by  means  of  the  reducing  gases,  both  inside  and  outside. 

Messerschmitt  has  proposed  to  use  compact  iron  (wrought  iron  or 
steel)  as  a  support  for  spongy  iron;  only  the  surface  layers  of  the  com- 
pact iron  taking  part  in  the  reaction.  The  spongy  iron  may,  for 
example,  be  placed  in  the  channels  of  a  number  of  iron  bars  of  U-shaped 
cross-section,  or  in  perforated  moulds,  tubes,  boxes  or  troughs  of 
compact  iron.* 

Elworthy  f  asserts  that  the  various  apparatus  proposed  for  the  pro- 
duction of  hydrogen  by  the  steam  and  iron  method  are  subjected  to 
serious  drawbacks  in  practice,  owing  to  the  liability  of  the  iron  to  cake 
together  and  to  its  difficulty  of  access  and  removal. 

The  iron  rapidly  cakes  and  chokes,  so  that  the  steam  or  gas  comes  into 
contact  with  only  a  small  proportion  of  the  active  surface  and  loss  of  efficiency 
results.  It  is  thus  frequently  necessary  to  remove  and  replenish  the  iron;  but  this 
is  a  troublesome  operation,  owing  to  the  construction  of  the  furnace  and  difficulty 
of  the  removal  of  the  iron.  Hence  Elworthy  places  the  iron  in  finely-divided  form 
in  a  large  number  of  separate  trays  of  refractory  fire-brick  or  the  like,  each  adapted 
to  contain  a  shallow  layer  of  iron  in  finely-divided  form  and  to  be  built  up  in  succes- 
sive layers  from  bottom  to  top  of  the  furnace,  so  as  to  form  a  close-lying  refractory 

*  British  Patent  12,117,  May  22,  1912. 
t  U.  S.  Patent  778,182,  Dec.  20,  1904. 


232 


THE  HYDROGENATION  OF  OILS 


filling  (Fig.  76).  The  trays  are  open  at  their  ends  to  enable  the  steam  or  gas  to 
pass  freely  over  them  in  contact  with  the  iron  when  built  up,  and  they  have  sup- 
porting flanges  for  supporting  the  under  face  of  one  tray  at  a  suitable  distance  from 
the  material  on  the  tray  below,  and  this  under  face  of  the  tray  radiates  a  quantity 
of  heat  onto  the  shallow  layer  of  metallic  iron  during  the  heat-absorbing  or  oxidizing 

stage,  while  at  the  same  time  super- 
heating the  steam  as  it  passes  along 
the  narrow  shallow  channel  between 
the  upper  and  lower  series  of  trays. 
When  the  trays  are  built  up  in  the 
furnace,  they  form  a  number  of  nar- 
row flues  containing  a  shallow  layer 
of  iron  and  running  in  a  zigzag  course 
from  bottom  to  top  of  the  furnace 
and  affording  free  passage  for  the 
steam  or  reducing  gas.  These  narrow 
flues,  so  to  speak,  divide  up  the  mass 
of  refractory  material  into  a  cellular 
structure  such  that  the  gases  can 
pass  freely  through  the  cell  flues  over 
the  iron. 

Messerschmitt  *  employs  spongy 
iron  produced  from  fragmentary  oxide 
iron  ore  (i.e.,  an  ore  containing 
Fe2Oa).  Only  spongy  iron  produced 
from  such  oxidized  iron  ore  is  re- 
garded by  Messerschmitt  as  pos- 
sessing the  requisite  porosity  and 
strength  for  carrying  out  the  proc- 
ess. 

The  effect  of  using  ferric  oxide  as  raw  material,  it  is  claimed,  is  that  the  oxide 
after  reduction  becomes  porous  throughout  its  entire  mass  on  account  of  the  de- 
crease in  volume  consequent  upon  the  removal  of  the  oxygen  therefrom  and  thus 
an  increased  surface  is  exposed  to  the  subsequent  action  of  the  steam.  The  use  of 
ferric  oxide  in  the  form  of  oxide  ores  is  important  because  the  lumps  of  this  ore,  in 
consequence  of  its  peculiar  natural  texture,  maintain  their  shape  in  spite  of  repeated 
reductions  and  oxidations  and  the  ore  possesses  the  necessary  strength  to  withstand 
the  pressure  of  superimposed  layers;  if  this  were  otherwise  the  path  for  the  gases 
would  become  choked  by  the  crumbling  of  the  ferric  oxide  and  continuous  working 
would  be  impeded.  The  gangue,  clay,  silica  and  other  components  of  the  ore  have 
for  effect  to  prevent  (in  spite  of  high  temperatures  which  may  be  produced  either 
intentionally  or  in  consequence  of  irregular  working  of  the  furnace)  a  sintering  of 
the  charge,  the  latter  thus  constituting  a  sort  of  rigid  incombustible  carrier  for  the 
oxides  and  the  iron  sponge. 

The  presence  of  carbon  monoxide  in  hydrogen  gas-mixtures  as  at  present  produced 
by  the  action  of  steam  on  reduced  iron  is  to  be  ascribed  to  the  following:  If  ferric 
oxide  be  reduced  by  means  of  carbon  monoxide  metallic  iron  and  carbon  dioxide 
are  formed,  but  simultaneously  a  considerable  quantity  of  carbon  is  precipitated 
from  the  carbon  monoxide.  Hence,  if  after  completion  of  the  reduction  phase  of 

*  U.  S.  Patent  971,206  of  Sept.  27,  1910. 


JPIG    76 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      233 

the  process,  steam  be  led  over  the  mixture  containing  spongy  iron  thereby  produced, 
there  is  produced  not  only  hydrogen  according  to  the  equation, 

3Fe  +  4H2O  =  Fe3O4  +  4H2| 

but  also  at  the  same  time  carbon  monoxide  and  carbon  dioxide  resulting  from  the 
reaction  of  the  steam  on  the  carbon  present,  thus  contaminating  the  hydrogen. 
Since  the  carbon  present  is  incompletely  decomposed  by  the  steam  at  the  compara- 
tively low  temperatures  used,  the  carbon  increases  more  and  more  by  the  repeti- 
tion of  the  cycles  (i.e.,  of  the  reduction  and  oxidation  phases  of  the  process)  and 
consequently  the  impurity  of  the  resulting  hydrogen  becomes  greater  and  greater. 
From  this  the  necessity  of  employing  means  for  the  prevention  of  the  precipitation 
of  carbon  during  the  reduction  phase  will  be  evident.  The  precipitation  of  carbon 
from  the  heated  carbon  monoxide  takes  place,  according  to  the  equation, 

=  C  +  C02. 


In  order  to  prevent  this  precipitation  of  carbon  the  following  method  is  used  by 
Messerschmitt: 

The  gases  destined  for  reduction  and  containing  carbon  monoxide  and  hydro- 
carbons are  mixed  with  a  quantity  of  steam  such  that  the  steam  volume  amounts, 
at  the  most,  to  half  of  the  volume  of  the  carbon  monoxide  plus  that  of  the  hydro- 
carbons. For  reducing  the  ferric  oxide  (or  Fe3O4)  this  mixture  may  be  directly  led 
into  the  retorts  or  tubes  containing  the  iron  oxide  without  a  considerable  amount  of 
carbon  being  precipitated.  The  reason  of  this  result  is  explained  as  follows:  If 
carbon  monoxide  be  mixed  with  steam,  hydrogen  and  carbon  dioxide  are  formed 
and  the  volume  of  the  first  is  the  same  as  that  of  the  carbon  monoxide  transformed 
into  dioxide  by  the  oxidation.  In  place  of  CO  therefore  an  equal  volume  of  H2  and 
an  equal  volume  of  CO2  is  formed  according  to  the  equation, 

CO  +  H2O  =  H2  +  CO2. 

In  general  the  reaction  with  hydrocarbons  is  as  follows: 

CmHn  +  2  mH2O  =  2  mH2  +  nH  +  mCO2. 

For  every  volume  of  hydrocarbon  therefore  one  volume  of  CO2  and  more  than 
two  volumes  of  hydrogen  are  formed.  Now  as  only  half  of  the  carbon  monoxide 
is  oxidized  by  the  steam  to  CO2  (since  the  amount  of  steam  added  is  only  half  that 
of  the  CO)  as  final  product  a  gas  of  the  following  composition  is  obtained  according 
to  the  equation, 

2  CO  +  H2O  =  CO  +  H2  +  C02. 

The  gas  used  for  reduction  of  the  iron  therefore  would  yield  for  every  volume  of 
carbon  monoxide  one  volume  of  hydrogen  and  one  volume  of  carbon  dioxide,  or 
for  two  volumes  of  reducing  gases  one  volume  of  carbon  dioxide.  This  proportion, 
however,  should  not  be  changed  on  account  of  the  reducing  gases  because  otherwise 
the  reduction  of  the  Fe3O4  to  metal  no  longer  takes  place.  For  this  reason  the 
addition  of  steam  is  restricted  according  to  the  above  equation  hi  order  that  the  gas 
and  steam  mixture  may  be  used  directly  for  the  reduction  of  the  iron.  This  reduc- 
ing gas  of  the  composition  CO  +  H2  -f  CO2,  however,  precipitates  considerably  less 
carbon  during  the  reduction  than  pure  carbon  monoxide  or  carbon  dioxide  mixed 
with  nitrogen  (producer  gas)  would  do.  The  reason  for  this  lies  in  the  presence  of 
the  hydrogen.  The  latter  first  attacks  the  ferric  oxide  with  the  formation  of  steam 


234  THE  HYDROGENATION  OF  OILS 

which  again  reacts  on  the  carbon  monoxide  and  thus  again  produces  hydrogen 
and  carbon  dioxide.  By  this  means  the  carbon  monoxide  tending  to  precipitate 
carbon  is  continually  reduced,  whereas  the  carbon  dioxide  and  the  hydrogen  (neither 
of  which  precipitates  carbon)  is  increased.  From  this  Messerschmitt  concludes 
that  the  presence  of  hydrogen  considerably  restricts  the  precipitation  of  carbon  from 
the  carbon  monoxide.  Hence  Messerschmitt  proposes  to  provide  for  the  addition  of 
steam  in  such  manner  that  its  volume  only  amounts  to  about  half  of  the  combined 
volume  of  the  carbon  monoxide  and  that  of  the  hydrocarbons  contained  in  the  gas. 
The  reduction  of  ferric  oxides  to  spongy  iron  by  means  of  reducing  gases  takes 
place  very  gradually,  the  iron  being  gradually  reduced  to  lower  stages  of  oxidation 
according  to  the  following  equations, 

3  Fe2O3  +  CO  =  2  Fe3O4  +  CO2, 

2  Fe3O4  +  CO  =     Fe«O7  +  CO2, 
Fe304  +  C0  =  3FeO     +  CO2, 

from  which  combinations  metallic  iron  is  formed  by  a  further  reduction  according 
to  the  equation, 

Fe6O7  +  7  CO  =  3  Fe2  +  7  CO2. 

A  surplus  of  reducing  gas  is  necessary  in  order  to  render  the  reduction  to  spongy 
iron  complete.  Since  between  the  products  of  oxidation  (CO2,  H2O)  produced  and 
the  reducing  gases  (CO,  H,  CnHm)  a  relationship  of  equal  weights,  according  to 
Messerschmitt,  subsists  which  is  not  affected  even  by  prolonged  reaction  on  the 
ore,  the  waste  gas  of  the  reduction  always  contains  a  considerable  amount  of  reduc- 
ing gases.  The  more  unfavorable  the  proportion  of  undecomposed  and  decomposed 
gases  in  the  waste  gases  becomes,  the  more  difficult  it  is  to  reduce  the  ore.  Reduc- 
tion takes  place  easily  at  the  beginning,  whereas  it  becomes  more  difficult  as  the  ore 
becomes  poorer  in  oxygen  and  the  further  reduction  to  spongy  iron  has  progressed. 
It  is  immaterial  for  the  production  of  the  hydrogen  whether,  during  the  reduction 
phase  metallic  iron  or  a  lower  stage  of  oxidation  than  that  of  black  oxide  of  iron  is 
produced,  since  Fe  as  well  as  FeO  and  Fe6O7  for  instance  are  oxidized  to  Fe3O4  when 
acted  on  at  incandescence  by  means  of  steam  while  giving  off  hydrogen  according 
to  the  formula, 

3  Fe  +  4  H2O  =  Fe3O4    +  4  H2, 
or 

Fe6O7  +  H2O     =  2  Fe3O4  +  H2. 

Now  it  has  been  found  that  the  proportion  of  the  gases  necessary  for  the  reduction 
relatively  to  the  hydrogen  produced  during  the  oxidation  phase  remains  relatively 
small  and  that  efficient  working  is  secured  if  the  reduction  of  the  ferric  oxide 
(Fe3O4)  during  the  reduction  phases  is  only  incompletely  effected  (at  most  only  half 
reduced). 

By  the  reaction  of  the  steam  during  the  oxidation  phase,  several  gases,  methane, 
carbon  dioxide  and  hydrocarbons,  are  formed  from  carbon  iron  combinations,  con- 
taminating the  hydrogen.  Absorption  of  carbon  is  impossible  as  long  as  (in  addition 
to  spongy  iron)  a  surplus  of  oxides  is  contained  in  the  ore.  If,  for  instance,  carbon 
were  actually  taken  up  it  would  of  necessity  have  to  be  decomposed  again  by  the 
oxygen  of  the  oxide  present,  according  to  the  equation, 

Fe.O7  +  C  =  6  FeO  +  CO. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS     235 


A  simple  form  of  apparatus  devised  by  Messerschmitt  *  is  shown 
in  Fig.  77.  The  contact  material  in  this  case  is  iron  in  the  form  of 
tubes.  These  are  shown  at  d  in  the  furnace  chamber  /.  The  tubes  d 
slip  over  the  upright  tubes  c  projecting  from  the  top  of  the  distrib- 
uting chamber  b.  A  filling  of  sand  around  the  base  of  these  tubes  d 
seals  them  and  yet  allows  their 
ready  removal  when  replacement 
is  required.  The  reducing  gas  is 
introduced  by  the  inlet  a.f 

In  another  type  of  furnace  for 
the  production  of  hydrogen  from 
reduced  iron  and  steam,  Messer- 
schmitt t  makes  use  of  apparatus 
as  shown  in  Fig.  78.  The  reaction 
is  carried  out  at  different  planes  in 
this  furnace.  The  walls  are  pro- 
vided at  different  heights  with 
heating  channels  cc.  The  gas  and 
air  nozzles  1,  2,  3  and  4  are  so  dis- 
posed that  the  heating  gases  are  discharged  tangentially  into  the 
furnace  in  such  a  manner  as  to  prevent  local  overheating  of  the  iron. 
The  oxidized  iron  in  the  different  zones  of  the  furnace  is  successively 
reduced  and  heated  and  the  waste  gases  from  one  zone  are  burned 
by  the  aid  of  a  blast  of  air  in  a  higher  zone.  In  the  upper  part  of 
the  structure  the  checkerwork  g  enables  preheating  of  the  reducing 
gas  and  steam. 

Natural  ores  of  manganese  or  of  manganese  and  iron  are  employed 
by  Messerschmitt  §  in  place  of  ordinary  iron  ore.  It  is  stated  that 
hydrogen  is  obtained  in  good  yields  at  700°  to  800°  C.  or  about  200 
degrees  lower  than  with  iron  sponge. 

*  Chem.  Ztg.  Rep.  (1913),  521. 

t  A  description  of  apparatus  recently  recommended  by  Messerschmitt  appears 
in  Chem.  Zeit.  Rep.  (1913),  696.  (German  Patents  266,863,  July  9,  1911,  and 
267,594,  Feb.  9,  1912.)  Messerschmitt  has  also  taken  out  German  Patent  268,339, 
Oct.  18,  1912,  supplementing  patent  No.  267,594.  (Chem.  Zeit.  Rep.  (1914),  31.) 
A  method  for  the  manufacture  of  hydrogen  by  the  alternate  oxidation  and  reduc- 
tion of  iron  is  described  by  Messerschmitt  in  German  Patent  268,062,  Nov.  3,  1912. 
(Chem.  Zeit.  Rep.  (1914),  22,  and  Zeitsch.  f.  angew.  Chem.  (1914),  47,  No.  5;  (1914), 
61,  No.  7.)  See  also  German  Patent  263,390,  July  24,  1912. 

t  Chem.  Zeit.  Rep.  (1913),  521;  German  Patent  263,391,  July  26,  1912. 

§  J.  S.  C.  I.,  1914,  201 ;  French  Patent  461,480,  Aug.  19, 1913.  Additional  methods 
employed  by  Messerschmitt  for  the  generation  of  hydrogen  are  described  in  J.  S.  C.  I., 
1914,  313. 


236 


THE  HYDROGENATION  OF  OILS 


An  apparatus  employed  by  the  Internationale  Wasserstoff-Aktien- 
Gesellschaft  is  shown  in  Fig.  79.  On  the  left  is  a  gas  producer  sup- 
plying fuel  gas  to  heat  the  two  vertical  retorts  shown  on  the  right. 
The  heating  gases  and  products  of  combustion  move  in  the  direction 
indicated  by  the  arrows  and  finally  pass  to  an  exit  flue.  The  valves 


FIG.  78. 


a  and  b  are  opened  and  water  gas  flows  through  the  iron  ore  filling  the 
retorts,  reducing  iron  oxide  to  finely-divided  metallic  iron.  When 
reduction  has  sufficiently  progressed  the  valves  a  and  6  are  closed  and 
the  three-way  valve  c  is  opened.  Steam  is  admitted  by  the  valve  d 
and  hydrogen  is  withdrawn  at  e.  When  the  iron  becomes  reoxidized 
the  steam  is  shut  off  and  the  oxide  again  reduced  by  water  gas.  The 
reducing  gases  after  passage  through  the  retorts  are  burned  in  the 
combustion  chamber.  The  hydrogen  exhibits  a  purity  approaching 
98  per  cent  at  a  cost  of  4  cents  per  cubic  meter.* 

The  above  concern  f  employs  iron  pyrites  waste  as  raw  material, 

*  Chemie  der  Gase,  Brahmer,  Frankfort  (1911),  93. 

f  It  should  be  stated  that  the  Internationale  Wasserstoff-Aktiengesellschaft  of 
Germany  is  the  owner  of  a  considerable  number  of  processes  and  patents  (Iwag 
System)  on  the  production  of  hydrogen. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS     237 


FIG.  79. 


FIG.  80. 


238  THE  HYDROGENATION  OF  OILS 

which  has  been  deprived  of  sulfur,  arsenic  and  zinc  by  roasting; 
this  material  is  porous  and  refractory  and  retains  these  properties 
after  repeated  use.* 

By  another  process  a  ferruginous  mass  is  treated  alternately  with 
steam  and  a  purified  reducing  gas,  both  of  which  are  preheated  in 
regenerators  situated  outside  the  reaction  furnace,  so  as  practically 
to  avoid  transference  of  heat  by  conduction  from  these  to  the  furnace. 
The  reducing  gas  leaving  the  reaction  furnace  is  burned  with  oxygen 
or  air  in  the  regenerators,  and  the  process  may  be  made  continuous 
by  employing  two  or  more  regenerators  with  a  central  furnace,  and 
passing  steam  and  gas  through  the  system,  first  in  one  and  then  in  the 
opposite  direction.! 

In  Fig.  80  is  shown  a  hydrogen-generating  apparatus  designed  by 
Strache.J  K  is  a  gas  producer,  the  gas  from  which  passes  through 
the  reaction  chamber  E,  containing  iron  filings,  and  is  burned  in  the 
checkerwork  R.  On  passing  steam  through  the  checkerwork  in  a 
reverse  direction  the  steam  becomes  superheated  and  when  brought 
into  contact  with  the  iron  filings  in  E  hydrogen  is  produced  and  is 
withdrawn  at  W.  Another  apparatus  designed  by  Strache  §  is  shown 
in  Fig.  81.  The  water-gas  generator  2,  provided  with  inlets  25  and  4, 
for  steam  and  air  respectively  is  connected  with  the  reaction  chamber 
6,  by  the  pipe  5,  provided  with  a  gas-discharge  pipe  24.  Just  above 
the  place  where  the  pipe  5  enters  the  reaction  chamber  is  a  baffle  22, 
and  on  the  opposite  side  of  the  chamber  is  a  similar  baffle  23.  A 
branch  from  the  air-supply  pipe  opens  just  below  the  baffle  22,  and 
similar  branches  open  at  8  and  9.  The  reaction  chamber  6  is  divided 
into  compartments  by  gratings  on  which  the  iron  reaction  material  is 
placed.  In  the  upper  part  of  the  chamber,  above  a  regenerator  10, 
are  purifying  retorts  11,  the  gas  to  be  purified  entering  by  20  and  the 
purified  product  leaving  by  21.  When  the  apparatus  has  been  brought 
to  the  proper  temperature  and  is  ready  for  the  production  of  hydrogen, 
steam  is  introduced  through  the  pipe  14,  below  the  valve  13,  so  as 
to  displace  any  gases  from  the  pipe  5  and  the  ash-pit  15.  Steam  is 
then  introduced  through  the  tube  18,  below  the  valve  12,  displacing 
gas  from  the  reaction  chamber  from  the  top  downwards.  The  hydro- 
gen produced  passes  away  through  19  to  a  holder,  from  which  it  may 
be  passed  through  the  pipe  20  into  the  purifying  retorts  11,  charged 
with  potash  lime. 

*  French  Patent  405,200,  July  19,  1909. 

t  British  Patent  2096,  Jan.  25,  1913,  Badische  Anilin  und  Soda  Fabrik. 

J  Brahmer,  Chemie  der  Gase,  91. 

§  German  Patent  253,705,  Oct.  26,  1910. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS     239 

The  claim  is  made  by  Dieffenbach  and  Moldenhauer  *  for  the  use 
of  the  residue  left  on  roasting  spathic  iron  ore  in  the  air,  in  the  prep- 
aration of  iron  to  be  employed  in  the  decomposition  of  steam.  This 
material  is  very  porous,  and  is  in  most  cases  free  from  substances 
which  would  have  injurious  effects  in  the  manufacture  of  hydrogen. 
They  also  claim  f  the  use  of  alloys  of  iron  with  manganese,  chromium, 
tungsten,  titanium,  aluminium  or  other  similar  elements  as  the  primary 
materials.  These  have  the  advantage  that  they  are  not  fusible,  do 


FIG.  81. 

not  soften,  and  do  not  form  fusible  or  soft  compounds  with  iron  or  its 
oxides.  In  place  of  alloys,  mixtures  of  iron  or  its  oxides  with  the  other 
elements  specified,  or  their  oxides,  may  be  employed,  for  instance  in 
the  form  of  briquettes. 

In  the  preparation  of  hydrogen  by  the  alternate  action  of  steam  on 
iron  and  of  reducing  gases  on  ferric  oxide,  the  iron  soon  loses  its  activity 
owing  to  fritting,  etc.  The  Badische  Anilin  und  Soda  Fabrik  t  claim 

*  German  Patent  232,347,  Feb.  6,  1910. 

t  French  Patent  444,044,  May  20,  1912.  See  also  Zeitsch.  f.  angew.  Chem.,  1914, 
No.  25,  222. 

t  French  Patent  440,780,  Feb.  29,  1912. 


240  THE  HYDROGENATION  OF  OILS 

as  remedies:  the  use  of  fused  iron  oxides,  especially  in  conjunction 
with  refractory  and  difficultly  reducible  oxides  of  high  melting-point 
such  as  magnesia  or  zirconia,  the  iron  oxides  being  prepared  by  the 
fusion  of  metallic  iron  in  the  presence  of  air  or  an  oxidizing  agent; 
fused  iron  oxides  may  be  used  in  conjunction  with  a  silicate  as  well  as 
similar  naturally  occurring  minerals  such  as  magnetite.  The  Badische 
Anilin  und  Soda  Fabrik  *  also  recommend  spongy  iron  prepared  by 
the  reduction  of  minerals  or  oxides  of  iron  by  means  of  carbon,  employ- 
ing external  heating.  The  metal  is  said  to  retain  its  porosity  after 
repeated  use.  "  Spongy  Swedish  iron,"  prepared  in  the  above  manner, 
is  especially  suitable. 

The  Berlin- Anhaltische  Maschinenbau-A-G.f  has  an  apparatus  for 
making  hydrogen  by  the  iron-sponge  system  which  considerably  facili- 
tates the  handling  of  the  ore  and  the  regulation  of  the  temperature. 

Belou  t  prepares  hydrogen  by  causing  steam  (preferably  super- 
heated) to  pass  over  red-hot  iron  in  retorts.  Hydrogen  and  oxide  of 
iron  are  thus  formed.  The  hydrogen  passes  on  to  a  gas  holder  for  use, 
and  the  oxide  is  reduced  to  metallic  iron  again  by  the  introduction  of 
charcoal  dust.  This  latter  operation  generates  so  much  heat  that  the 
retort  is  again  immediately  ready  for  decomposing  steam.  By  using 
a  number  of  retorts  and  carrying  on  the  two  processes  of  decomposi- 
tion and  revivification  alternately,  the  production  of  hydrogen  may 
be  made  continuous.  Suitable  provision  is  made  for  the  removal  of 
the  carbon  monoxide  and  dioxide  formed  during  the  revivification. 

Highly-heated  tubes  of  refractory  earthenware,  partly  filled  with  iron  filings,  and 
in  which  a  partial  vacuum  has  been  previously  produced,  are  used  by  Oettli  (British 
Patent  16,759,  Sept.  4,  1885).  A  certain  proportion  of  hydrogen  is  added  to  the 
steam,  and  this,  together  with  the  action  of  the  iron  filings,  is  claimed  to  tend  to 
destroy  the  equilibrium  conditions  and  to  prevent  the  hydrogen  formed  by  the 
decomposition  of  the  steam  from  re-uniting  with  oxygen.  This  effect  is  said  to  be 
promoted  by  the  reduced  pressure  in  the  tubes,  and  by  the  loss  of  heat  due  to  the 
splitting  up  of  the  aqueous  vapor.  From  the  tubes  the  gases  pass  through  separators 
to  gas  holders. 

Vignon's  apparatus  §  consists  of  a  set  of  retorts  containing  iron 
oxide.  A  reducing  gas  is  led  from  a  gas  producer,  through  a  suitable 
purifier,  into  the  retorts  for  the  reduction  of  the  iron  oxide.  The  heat 
formed  thereby  is  utilized  for  the  regenerative  heating  of  the  air 
blast  for  the  producer.  The  heat  of  the  hydrogen  gas  produced  is  used 
for  superheating  the  steam.  A  set  of  four  valves  can  be  manipulated 

*  French  Patent  453,077,  Jan.  11,  1913. 

t  J.  S.  C.  I.,  1914,  256,  and  British  Patent,  28,390,  Dec.  9,  1913. 

j  British  Patent  7518,  May  25,  1887. 

§  First  Addition,  dated  Dec.  27,  1907,  and  French  Patent  373,271,  Jan.  2,  1907. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS     241 

by  a  single  handle,  allowing  the  regulating  and  reversing  of  the  differ- 
ent gas  currents. 

The  process  of  Gerhartz  *  consists  in  blowing  steam  through  a 
molten  oxidizable  metal,  and  subsequently  reducing  the  oxidized  metal 
for  further  use.  Molten  iron,  for  example,  is  introduced  into  a  vessel 
lined  with  refractory  material  and  provided  with  a  perforated  false 
bottom  somewhat  after  the  manner  of  the  Bessemer  converter.  Steam 
under  pressure  is  blown  into  the  space  below  the  false  bottom  and  is 
decomposed  while  rising  through  the  molten  iron;  the  hydrogen  pro- 
duced is  led  off  through  a  suitable  pipe,  and  the  heat  carried  by  it  is 
utilized  for  generating  steam.  The  fluidity  of  the  molten  iron  is 
gradually  diminished,  and  after  a  time  the  supply  of  steam  is  stopped, 
coke  is  introduced  and  the  melt  is  blown  with  air  in  order  to  reduce 
the  iron  oxide  which  has  been  formed  and  thus  restore  the  fluidity  of 
the  molten  mass. 

A  process  brought  forward  by  The  Nitrogen  Co.f  involves  reacting 
with  steam  on  a  molten  or  heated  metal  having  a  strong  affinity  for 
oxygen,  which  is  thus  absorbed.  After  collecting  the  residual  hydro- 
gen, the  metallic  oxide  produced  is  made  to  dissolve  or  disseminate  in 
a  body  of  fused  salt  in  which  it  is  brought  into  contact  with  a  suitable 
reducing  agent,  the  reduced  metal  being  continuously  returned  for 
re-oxidation  in  the  process. 

Illuminating  gas,  water  gas  or  other  gas  containing  free  hydrogen, 
according  to  Jaubert,  is  passed  through  retorts  packed  with  briquettes 
formed  of  iron  oxide  with  a  refractory  substance  and  a  catalytic  agent, 
the  retorts  being  heated  to  800°  to  900°  C.f  Steam  is  afterwards 
passed  through  the  retorts  at  the  same  temperature,  yielding  hydrogen. 
The  briquettes  are  preferably  composed  of  a  mixture  of  30  to  60  kilos 
of  iron  oxide  (Fe2O3  or  Fe304),  15  to  25  kilos  of  fire  clay  or  pumice,  15 
to  25  kilos  of  calcined  magnesia  and  5  to  15  kilos  of  the  oxide  of  lead 
copper,  chromium  or  manganese. 

The  decomposition  of  water  into  hydrogen  and  oxygen  by  the  action  of  con- 
centrated solar  rays  in  presence  of  finely-divided  iron  and  apparatus  for  effecting 
this  is  described  by  Claver.§ 

In  the  manufacture  of  hydrogen  by  alternately  passing  steam  over 
iron,  and  water  gas  over  the  iron  oxide  thus  formed,  Caro  ||  has  devised 
a  system  by  which  portions  of  the  water  gas  are  burned  in  different 

*  German  Patent  226,543,  June  23,  1909. 

t  British  Patent  17,666,  Aug.  3,  1911. 

j  Jaubert,  French  Patent  418,312,  Sept.  23,  1909. 

§  British  Patent  21,468,  Nov.  12,  1895. 

II  German  Patent  249,269,  Aug.  30,  1910. 


242  THE  HYDROGENATION  OF  OILS 

parts  of  the  reaction  chamber,  so  that  in  addition  to  the  reduction  of 
the  iron  oxide,  a  superheating  of  the  reduced  iron  is  effected.  It  is 
claimed  that  by  working  in  this  manner,  the  gas-making  period  can  be 
considerably  prolonged. 

Steam  and  hydrocarbons  (such  as  those  derived  from  iron  carbides) 
are  passed  over  red-hot  iron  which  has  been  mixed  with  (preferably 
5  to  10  per  cent  of)  copper,  lead,  vanadium  or  aluminium,  either  to- 
gether or  separately.  These  metals  according  to  Saubermann  *  cata- 
lytically  accelerate  the  reaction  between  steam  and  iron,  and  also 
decompose  the  hydrocarbons. 

The  action  of  mixtures  of  carbon  monoxide  and  hydrogen  on  iron 
oxides  is  discussed  by  Gautier  and  Clausmann.f  They  passed  a 
mixture  of  3  volumes  of  carbon  monoxide  and  1  volume  of  hydrogen 
at  500°  C.  over  the  ferroso-ferric  oxide  derived  from  the  calcination 
of  a  native  ferrous  carbonate.  The  substance  formed  contained  about 
7  per  cent  of  carbon,  and  93  per  cent  of  ferrous  oxide  and  iron  carbides 
in  approximately  equal  proportions.  When  steam  was  passed  over 
this  substance  at  400°  C.,  a  gas  was  obtained  containing  96  per  cent 
of  hydrogen  and  4  per  cent  of  methane.  Over  iron  (reduced  from  the 
oxalate  spread  over  pumice)  at  1250°  C.  was  passed  a  mixture  of  2 
volumes  of  carbon  dioxide  and  1  volume  of  hydrogen.  The  issuing 
gas,  besides  23  per  cent  of  carbon  monoxide  and  76  per  cent  of  hydro- 
gen, contained  0.15  per  cent  methane. 

*  British  Patent  401,  Jan.  6,  1911. 
t  Compt.  rend.  (1910),  151,  355. 


CHAPTER  XVII 
ACTION   OF  ACIDS   ON   METALS 

One  of  the  oldest  methods  of  generating  hydrogen  and  one  which  is 
to-day  commonly  used  in  the  laboratory  and  for  the  production  of 
hydrogen  on  the  small  scale  is  that  of  acting  on  metals  with  acids, 
iron  or  zinc  and  sulfuric  acid  being  the  materials  usually  employed. 
The  cost  of  generation  in  this  manner  is  too  high  to  permit  of  large 
scale  operations  except  in  those  cases  where  hydrogen  is  obtained  as 
a  by-product  in  the  preparation  of  metallic  salts.  Accordingly  this 
method  of  hydrogen  generation  will  be  considered  only  very  briefly. 

Carulla  endeavors  to  prepare  alkali  salts,  hydrogen  and  iron  oxide, 
the  gas  being  generated  by  the  action  of  hydrochloric  acid  on  iron. 
Instead  of  using  water  alone  for  the  absorption  of  hydrochloric  acid 
in  the  Le  Blanc  process,  some  or  all  of  the  receivers  or  towers  are 
packed  with  scrap  iron  or  mild  steel,  ferrous  chloride  being  thus  formed 
and  hydrogen  evolved.  The  chloride  is  then  converted,  by  precipita- 
tion, into  iron  oxide  *  and,  since  very  dilute  solutions  are  preferable 
for  this  purpose,  the  absorption  of  the  last  traces  of  hydrochloric 
acid  is  rendered  very  easy  by  this  process,  the  ferrous  liquor  plant 
being  conveniently  placed  at  the  end  of  the  system,  and  hydrochloric 
acid  of  high  strength  being  produced,  if  desired,  in  intermediate  parts 
of  the  plant. 

According  to  Barton  f  dilute  sulfuric  acid  is  allowed  to  act  on  zinc 
and  the  zinc  sulfate  solution  produced  is  filtered  and  mixed  with  a 
solution  of  sodium  carbonate  or  bicarbonate,  thus  giving  a  precipitate 
which  is  separated,  washed  and  dried,  and  sodium  sulfate  which  is 
also  recovered. 

The  insoluble  zinc  precipitate  is  proposed  as  "an  excellent  substitute  for  oxide 
of  zinc  used  in  the  paint  and  rubber  industries."  The  apparatus  claimed  consists 
of  a  generating  vessel,  communicating  with  an  acid  tank  by  a  feed  pipe  and  a  return 
pipe,  and  also  with  a  gasometer  and  a  mixing  tank,  the  latter  receiving  the  zinc 
sulfate  solution  from  the  generator  and  sodium  carbonate  solution  from  another 
vessel  and  communicating,  in  its  turn,  with  a  centrifugal  separating  and  washing 
apparatus.  The  generator  may  be  fitted  with  electrodes  for  the  production  of 
electrical  energy. 

*  e.  g.,  as  in  British  Patent  27,302,  1908;  J.  S.  C.  I.,  1909,  1126. 
t  British  Patent  28,534,  Dec.  8,  1910. 

243 


244  THE  HYDROGENATION  OF  OILS 

An  apparatus  arranged  to  generate  electrical  energy  when  zinc  is  being  dis- 
solved in  sulfuric  acid  to  produce  hydrogen  is  set  forth  by  Eastwick  (British  Patent 
10,228,  April  27,  1911).  The  apparatus,  which  is  intended  specially  for  the  gener- 
ation of  hydrogen  by  the  action  of  zinc  on  dilute  sulfuric  acid,  consists  of  a  gen- 
erating chamber,  with  false  bottom,  on  which  rests  the  metal  to  be  acted  upon, 
and  a  liquid-collecting  chamber  situated  below.  The  acid  is  delivered  by  gravitation 
into  contact  with  the  metal  at  a  point  near  to,  but  above,  the  false  bottom,  and  the 
salt  solution  produced  runs  through  into  the  collecting  chamber.  An  electrode 
may,  if  desired,  be  immersed  in  the  liquid,  within  or  below  the  reaction  chamber,  so 
that  the  apparatus  may  serve  also  as  an  electric  cell.  An  apparatus  described  by 
way  of  example  comprises  superposed  chambers  contained  within  a  single  casing, 
the  uppermost  (containing  zinc)  and  the  intermediate  chamber  being  provided 
with  porous  or  perforated  false  bottoms.  Acid  is  conducted  to  the  first  chamber  by 
a  pipe  which  reaches  down  through  the  upper  layers  of  zinc  into  a  cage  having  lateral 
perforations,  and  any  excess  of  pressure  forces  the  acid  back  in  the  supply  pipe,  but 
the  zinc  sulfate  solution  produced  percolates  into  the  lowermost  chamber.  A  zinc 
rod  or  plate,  to  act  as  electrode,  is  placed  above  the  false  bottom  in  the  first  chamber 
and  a  copper  electrode  in  the  intermediate  chamber,  so  that,  with  the  descending 
liquid,  an  electric  cell,  suitable  for  electro-plating  work,  etc.,  is  produced,  this  also 
ensuring  the  decomposition  of  any  free  acid  in  the  spent  liquid. 

Hydrogen  gas  is  obtained  by  Pratis  and  Marengo  *  by  acting  upon 
iron  filings  and  water  by  gradual  additions  of  sulfuric  acid  of  50°  Be., 
equal  parts  by  weight  being  taken  of  each.  The  hydrogen  produced 
is  conducted  first  through  water,  then  through  a  solution  of  a  lead  salt, 
and  through  a  device  containing  diaphragms  of  wire  gauze,  to  a  gasom- 
eter, whence  the  gas  traverses  an  insulating  water  valve,  an  elastic 
chamber  and  a  second  device  similar  to  the  first,  when  it  is  taken  by 
branch  pipes  to  the  place  of  utilization.  The  arrangements  described 
permit  of  the  gas  being  produced  under  considerable  pressure. 

To  overcome  the  difficulties  in  the  way  of  generating  hydrogen  from  sulfuric 
acid  and  iron,  Pratis  and  Marengo  (British  Patent  15,509,  June  29,  1907)  propose 
to  employ  the  following  approximate  proportions,  by  weight: 

Broken  iron,  5  parts;  water,  5  parts;  50°  Be.  sulfuric  acid,  5.8  parts;  these  being 
found  to  produce  a  pasty  non-caking  residue,  easy  to  remove  from  the  apparatus  and 
to  work  up  for  the  manufacture  of  ferrous  sulfate  or  Nordhausen  sulfuric  acid. 

The  apparatus  consists  of  a  generating  cylinder,  fitted  with  a  valve  for  discharg- 
ing the  residue.  The  acid  and  water  are  run  in  on  to  the  charge  of  iron  from  reser- 
voirs at  a  higher  level,  the  supply  valve  being  controlled  by  the  bell  of  the  gas  holder, 
and  is  self-closing  when  the  bell  sinks  below  a  certain  level;  or,  if  the  gas  is  to  be  col- 
lected in  receivers  at  high  pressure,  the  full  charge  of  liquids  may  be  added  at  once. 
Purifiers  are  arranged  between  the  generator  and  gas  holder,  and  an  excessive  rate 
of  generation  is  prevented  by  gas  checks,  which  cause  an  increase  of  pressure  in  the 
generator,  whereby  the  acid  is  driven  back  in  the  supply  pipe  and  the  evolution  of 
gas  diminished. 

*  British  Patent  16,277,  July  22,  1896. 


ACTION  OF  ACIDS  ON  METALS  245 

The  reaction  which  takes  place  in  the  spontaneous  formation  of 
iron  rust, 

C02  -I-  H20  +  Fe  +  FeC03  +  H2 

may  be  accelerated  by  agitation,  etc.,  so  as  to  become  a  practicable 
method  according  to  Bruno  *  for  the  production  of  hydrogen.  Frag- 
ments of  cast  iron  or  steel  or  iron  filings  were  introduced  together 
with  water  into  a  steel  bottle  and  carbon  dioxide  was  passed  in  until 
the  air  was  displaced  and  the  liquid  was  saturated  with  the  gas. 
The  bottle  was  then  closed  by  a  steel  cover,  and  placed  in  an  appa- 
ratus where  it  made  about  2000  revolutions  per  hour.  There  was  no 
appreciable  change  in  the  pressure  inside  the  vessel,  and  after  36  to 
40  hours  the  gas  withdrawn  from  the  bottle  consisted  of  pure  hydro- 
gen. At  the  end  of  20  hours  the  gas  consisted  of  about  two-thirds 
of  hydrogen  and  one-third  of  carbon  dioxide. 

*  Bull.  Soc.  Chim.  (1907),  1,  661. 


CHAPTER  XVIII 

MISCELLANEOUS   METHODS   OF  HYDROGEN 
GENERATION 

Much  attention  has  been  given  to  the  production  of  hydrogen  by 
chemicals,  which,  when  added  to  water  or  hydrated  substances,  would 
liberate  hydrogen  freely,  thus  enabling  the  generation  of  hydrogen 
at  any  point  without  the  necessity  of  setting  up  elaborate  apparatus. 
Powdered  aluminium  or  silicon  and  alkali,  "  activated  "  aluminium 
and  water,  ferrosilicon  and  calcium  hydrate,  calcium  hydride  and  the 
like  have  been  proposed  under  various  names  such  as  hydrone,  hydro- 
genite,  the  Hydrik  process,  etc.  Bergius  has  brought  out  a  novel 
process  involving  the  treatment  of  carbon  or  iron  with  water  in  a 
liquid  condition  under  very  high  pressures.  The  following  indicate 
the  principal  developments  in  this  direction. 

Foersterling  and  Philipp  *  generate  hydrogen  by  causing  water,  in 
a  finely-divided  state,  to  react  successively  with  relatively  small 
masses  of  sodium,  separated  from  each  other,  in  the  same  containing 
vessel,  in  such  a  way  that  the  supply  of  hydrogen  is  continuous,  and 
at  a  rate  that  substantially  prevents  a  solution  being  formed.  They 
also  propose  silicides  for  the  generation  of  hydrogen. f  An  intimate 
mixture  of  equal  parts  by  weight  of  sodium  and  aluminium  silicide 
("  sical  ")  is  prepared  by  heating  the  two  substances  in  a  kneading 
machine  until  all  the  sodium  is  molten;  the  kneading  appliance  is 
then  put  into  operation  and  kept  continuously  rotating  while  the 
mixture  cools  down,  after  which  the  latter  is  transferred  to  a  press 
and  briquetted.  One  kilo  of  the  mixture,  when  acted  on  by  water, 
generates  about  700  liters  of  hydrogen,  the  reaction  being  represented 
by  the  equation, 

Al2Si4  +  8  Na  +  18  H2O  =  A12(OH)6  +  4  Na2Si03  +  15  H2. 

Brindley  and  Bennie  (U.  S.  Patent  943,036,  Sept.  14,  1909)  use  a  mixture  con- 
sisting of  finely-divided  aluminium  and  molten  sodium  hydroxide,  the  proportion 
of  the  latter  being  between  1  and  3  mols.  to  1  mol.  of  aluminium.  Silicon  and  zinc 
may  also  be  added. 

Brindley  (U.  S.  Patent  909,536,  Jan.  12,  1909)  treats  an  alkali  or  alkaline-earth 
metal,  for  example  sodium,  in  a  finely-divided  state,  with  a  crude  hydrocarbon  oil 

*  U.  S.  Patent  883,531,  March  31,  1908. 
t  U.  S.  Patent  977,442,  Dec.  6,  1910. 
246 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION     247 

or  similar  substance,  which  will  temporarily  prevent  oxidation  of  the  metal,  and  with 
an  inert  substance  such  as  infusorial  earth,  and  the  mixture  is  compressed  into  tablets 
or  briquettes,  which  when  brought  into  contact  with  water  will  generate  hydrogen. 
In  order  to  increase  the  yield  of  hydrogen,  a  metal  (aluminium,  silicon)  which  forms 
a  hydroxide,  the  hydrogen  of  which  can  be  replaced  by  an  alkali  or  alkaline-earth 
metal,  is  also  incorporated  in  the  mixture. 

Philipp  (U.  S.  Patent  1,041,865,  Oct.  22,  1912)  generates  hydrogen  by  the  action 
of  water  on  a  mixture  of  metallic  sodium  and  aluminium  silicide.  The  action  of 
water  on  this  mixture  does  not  proceed  to  completion,  and  the  method  consists  in 
first  treating  the  mixture  with  water,  and  then  passing  the  hot  hydrogen  and  steam 
through  a  similar  mixture  which  has  previously  been  partially  decomposed  by 
treatment  with  water. 

Jaubert  *  suggests  that  the  hydrogen  evolved  in  such  industrial 
processes  as  the  production  of  electrolytic  soda,  be  collected,  deprived 
of  any  oxygen  present  (as  by  passage  over  red-hot  copper),  dried, 
directed  into  an  iron  tube  charged  with  calcium  in  small  pieces,  and 
heated  for  some  hours  to  redness.  The  dark  grey  calcium  hydride 
thus  obtained  is  preserved  in  closed  vessels.  When  the  hydride  is 
brought  into  contact  with  cold  water,  there  is  a  violent  evolution  of 
hydrogen. 

Bamberger,  Bock  and  Wanz  f  generate  hydrogen  from  calcium 
hydride  which  is  mixed  with  substances  such  as  gypsum,  sodium  bi- 
carbonate, soda-lime  or  boric  acid,  which  contain  water  or  carbonic 
acid,  but  which  react  only  when  heated  to  about  80°  C.,  or  a  higher 
temperature. 

Gases  which  are  prepared  by  the  action  of  a  liquid  upon  a  solid,  for  instance, 
hydrogen  by  the  action  of  water  on  calcium  hydride,  are  obtained  pure  and  free 
from  the  water  vapor  which  is  frequently  generated  by  the  heat  of  the  reaction, 
in  the  following  manner:  The  solid  is  placed  in  a  connected  series  of  separate 
vessels,  or  in  superposed  compartments  of  the  same  vessel,  and  the  liquid  is  ad- 
mitted to  the  first,  or  lowest,  of  the  series.  The  gas  given  off,  along  with  some 
vapor  of  the  liquid,  passes  through  the  next  vessel,  or  compartment,  and  so  through 
the  series  and  leaves  the  last  in  a  dry  condition,  the  water  vapor  having  been  re- 
tained by  the  fresh  material.  When  the  first  vessel  is  exhausted  it  is  recharged 
and  connected  to  the  end  of  the  series,  the  second  vessel  becoming  the  first.  In 
this  way  the  process  becomes  continuous. t 

Schwarz  §  describes  two  simple  methods  for  preparing  pure  hydro- 
gen gas  and  carbonic  oxide.     On  heating  a  mixture  of  zinc  dust  and 
calcium  hydrate  gradually  in  a  combustion  tube,  a  constant  current 
of  pure  hydrogen  is  liberated  according  to  the  equation, 
Zn  +  CaH2O2  =  ZnO  +  CaO  +  H2. 

*  French  Patent  327,878,  Dec.  31,  1902. 
t  German  Patent  218,257,  March  31,  1908. 
J  Jaubert,  French  Patent  381,605,  Nov.  14,  1907. 
§  Ber.,  19,  1140. 


248  THE  HYDROGENATION  OF  OILS 

On  mixing  the  zinc  dust  with  calcium  carbonate  in  molecular  pro- 
portions and  heating  as  before,  pure  carbonic  oxide  gas  is  evolved 
thus: 

Zn  +  CaCO3  =  ZnO  +  CaO  +  CO. 

In  both  cases  nearly  theoretical  quantities  of  gas  are  obtained. 

Hydrogen  is  produced  by  the  process  of  Jaubert  *  by  ignition  and 
autocombustion  in  a  closed  generator,  of  a  mixture  consisting  of  an 
excess  of  a  combustible  substance  (metal,  metalloid  or  alloy),  capable 
of  decomposing  steam  at  a  high  temperature,  an  oxidizer  or  other 
substance  to  maintain  the  combustion,  and  a  substance  evolving 
steam  on  heating  (which  is  omitted,  partially  or  wholly,  if  steam  be 
introduced  from  an  external  source). 

Suitable  mixtures,  which  may  be  packed  in  metal  cartridges,  to  be  opened  and 
placed  directly  in  the  generator,  are  the  following:  (a)  Powdered  iron  20  kilos,  slaked 
lime  10,  potassium  perchlorate  6,  (6)  ferrosilicon,  with  75  per  cent  of  silicon,  20, 
litharge  10,  soda-lime,  containing  two-thirds  of  sodium  hydroxide  60;  (c)  ferrosilicon 
20,  powdered  iron  5,  wheat  flour  3,  lime  5,  and  potassium  chlorate  3.  If  the  ingre- 
dient evolving  steam  be  omitted,  the  generator  may  be  surrounded  by  a  water 
jacket,  the  two  vessels  being  connected  so  that  the  necessary  steam  is  supplied  from 
the  latter  by  the  heat  of  the  reaction;  a  pipe  from  the  generator  conveys  the  gas 
either  to  the  exterior  or  through  a  purifying  and  drying  apparatus,  to  be  utilized. 
The  generator  described  is  closed  by  a  heavy  lid  which,  for  safety,  is  held  in  position 
by  its  own  weight. 

The  Hydrogenit  process  of  Jaubert  f  involves  mixing  finely-powdered 
ferrosilicon  with  soda-lime  to  produce  a  grayish  granular  mass  which 
easily  ignites  and  burns  readily  even  with  the  exclusion  of  air,  the 
reaction  being 

Si  +  Ca(OH)22  NaOH  =  Na2Si03CaO  +  2  H2. 

From  3  kilos  of  the  mixture,  which,  by  the  way,  is  stable  at  ordinary 
temperature,  about  1  cubic  meter  of  very  pure  hydrogen  is  obtained. 
The  mixture  is  pressed  to  blocks  and  is  shipped  in  metal  containers 
holding  25  to  50  kilos,  affording  8  to  16  cubic  meters  hydrogen  in 
about  a  ten-minute  period.  The  mixture  is  kindled  by  a  small  amount 
of  ignition  powder  or  quick-match.  Equipments  for  furnishing 
150  cubic  meters  hydrogen  per  hour  have  been  made.  The  gener- 
ators are  arranged  in  pairs,  see  Fig.  82. 

A  case  of  hydrogenit  is  placed  in  each  generator.  The  cover  of  the  generator  is 
put  on  and  clamped  in  place  and  the  mixture  lighted  through  a  closable  opening 
in  the  cover.  The  generators  are  equipped  with  water  jackets  and  the  steam  pro- 
duced by  the  heat  of  the  reaction  is,  towards  the  end  of  the  run,  turned  into  the 

*  French  Patent  427,191,  May  21,  1910. 
t  German  Patent  236,974. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION    249 

generator,  giving  a  larger  yield  of  hydrogen.     The  gas  is  washed  and  dried.     One 
cubic  meter  of  hydrogen  made  from  Hydrogenit  costs  about  32  to  38  cents.* 

Jaubert  (French  Patent  422,296,  Jan.  14,  1910)  has  described  the  following 
modification  of  the  above.  Metals  such  as  aluminium  or  zinc,  or  their  alloys,  or 
metalloids  such  as  silicon  or  carbon,  or  their  compounds,  e.g.,  ferrosilicon,  when 
mixed  with  alkali  or  alkaline-earth  hydroxides  in  the  form  of  dry  powders,  yield 
mixtures  quite  stable  at  ordinary  temperatures.  If,  however,  reaction  be  induced 
by  local  application  of  heat,  hydrogen  is  evolved  and  sufficient  heat  is  developed 
to  cause  the  propagation  of  the  reaction  throughout  the  mass.  A  suitable  appara- 


FIG.  82. 


tus  consists  of  a  tube  closed  at  one  end  by  a  screw  cap  and  having  near  this  end  an 
opening  (with  a  screw  cap)  through  which  a  quick-match  or  piece  of  hot  iron  may 
be  introduced  to  induce  the  commencement  of  the  reaction.  The  other  end  of  the 
tube  is  formed  by  a  perforated  plate,  through  which  the  hydrogen  evolved  passes 
into  a  chamber  packed  with  filtering  material,  and  thence  into  an  annular  space 
formed  between  the  tube  and  a  jacket  extending  nearly  the  whole  length  of  the  latter. 
The  hydrogen  accumulates  in  this  annular  space  under  pressure,  and  is  withdrawn 
as  required  through  a  suitable  outlet. 

Ferrosilicon  containing  75  per  cent  of  silicon,  when  heated  to  a  very  high  temper- 
ature is  capable  of  decomposing  steam  with  sufficient  evolution  of  heat  to  carry  on 
the  reaction, 

3  FeSi«  +  40  H2O  =  Fe3O4  +  18  SiO2  +  40  H2. 

(Jaubert,  French  Patent  438,021,  March  4,  1911.)  The  reaction  may  be  regulated 
by  the  addition  of  lime,  which  has  the  further  advantage  of  forming  an  easily-work- 
able slag.  The  apparatus  comprises  a  refractory  chamber  surrounded  by  a  steam 
coil,  the  delivery  end  of  which  terminates  in  a  series  of  injectors,  which  admit  steam 

*  Zeitsch.  f .  angew.  Chem.  (1912),  2405. 


250  THE  HYDROGENATION  OF  OILS 

into  the  chamber;  a  feeding  hopper  is  provided  at  the  top  of  the  chamber  and  a  door 
for  the  withdrawal  of  the  slag  at  the  bottom. 

An  alkali  or  alkaline-earth  hydroxide,  or  a  mixture  of  the  two,  is  mixed  with 
charcoal  and  a  finely-divided  metal  or  mixture  of  metals,  and  the  whole  is  heated 
in  a  hermetically-sealed  vessel,  with  the  exclusion  of  air,  and  under  diminished  pres- 
sure. Under  the  action  of  the  metal,  according  to  Hlavati  (German  Patent  250,128, 
Feb.  25,  1911)  the  hydroxide  is  converted  into  oxide,  and  hydrogen  and  carbon 
monoxide  are  formed. 

The  Siemens  &  Schuckert  Company  has  worked  out  a  process  for 
the  production  of  hydrogen  from  the  reaction  between  silicon  and 
caustic  soda  solution.  Formerly  steam  was  employed,  but  now  the 
heat  set  free  during  the  reaction  is  utilized  for  maintaining  the  proper 
conditions.  The  evolution  of  hydrogen  gas  takes  place  when  a  25  per 
cent  solution  of  caustic  soda  acts  on  silicon  introduced  in  small  quan- 
tities. The  capacity  of  a  transportable  plant  is  60  to  120  cubic  meters 
per  hour,  while  stationary  plants  are  built  for  capacities  up  to  300  cubic 
meters  per  hour.  The  process  is  a  neat  one,  but  the  cost  is  about 
18.75  cents  per  cubic  meter.* 

A  somewhat  similar  system  is  used  in  France  under  the  name  of 
the  Silicol  process.  Ferrosilicon  or  other  silicon  alloy  is  treated  with 
freshly-prepared  35  to  40  per  cent  caustic  soda  solution.  The  heat 
of  solution  of  the  alkali  raises  the  temperature  to  60  to  80  degrees  and 
enables  the  reaction  to  progress  rapidly.  Hydrogen  by  this  method 
costs  about  20  cents  per  cubic  meter. f 

By  the  Hydrik  process  aluminum  powder  is  acted  on  by  caustic 
soda  giving  hydrogen  and  sodium  aluminate,  according  to  the  equa- 
tion, 

2  Al  +  6  NaOH  =  2  Al(ONa)3  +  3  H2. 

Fig.  83  shows  a  gas  generator  for  the  Hydrik  process  with  an  hourly 
capacity  of  10  cubic  meters. 

By  the  addition  of  lime,  or  calcium  compounds  that  form  lime, 
according  to  t  Consortium  fur  Elektro-chem.  Ind.  ges.  m.  b.  H., 
nearly  the  full  theoretical  quantity  of  hydrogen  is  rapidly  liberated 
on  heating  silicon  in  an  aqueous  solution  of  caustic  alkali.  The  process 
may  be  carried  out  in  an  iron  generator  fitted  with  stirrers,  and  in 
British  Patent  11,640,  May  13,  1911,  it  is  stated  that  the  temperature 
necessary  for  the  generation  of  hydrogen  from  silicon  and  caustic 
alkali  solutions  may  be  obtained  by  the  solution  of  the  powdered  alkali 
or  alkali  oxides  in  water,  or  by  the  heat  produced  in  the  chemical 
reaction  between  aluminium  or  aluminium  alloys  and  the  alkali. 

*  Met.  and  Chem.  Eng.  (1911),  157. 

t  See  Zeitsch. f .  angew.  Chem.  (1912),  2405. 

J  British  Patent  21,032,  Sept.  14,  1909. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION     251 


Jaubert  (French  Patent  430,302,  Aug.  6,  1910)  uses  a  strong  solution  of  a  caustic 
alkali,  or  a  solution  of  sodium  or  potassium  sulfate  containing  such,  which  is  made 
to  act  upon  a  compound  or  alloy  of  silicon  (preferably  ferrosilicon,  manganosilicon 
or  silicospiegel)  in  such  a  way,  that  the  heat  produced  in  preparing  the  alkali  solu- 
tion is  utilized  in  effecting  the  reaction,  no  external  heat  being  required.  The  reac- 
tion takes  place  in  a  generating  vessel,  fitted  with  a  stirring  device  and  surmounted 
by  a  feeding  hopper  containing  the  powdered  alloy;  this  vessel  communicates  both 
with  an  arrangement  for  washing  and  cooling  the  gas  and  with  another  vessel,  also 
provided  with  a  stirrer,  in  which  the  solution  of  caustic  alkali  is  prepared  (e.g.,  by 
dissolving  1  part  by  weight  of  sodium  hydroxide  in  1^  to  2  parts  of  water).  The 


FIG.  83. 

water  which  has  served  to  cool  the  gas  in  the  condenser  passes  either  to  the  generator 
or  to  the  dissolving  vessel.  A  strong  solution  of  alkali  being  used,  an  acid  silicate 
is  obtained;  moreover,  non-caustic  residues,  suitable  for  use  in  dyeing  and  bleach- 
ing, are  obtained. 

The  preparation  of  hydrogen  under  pressure  by  the  wet  method  is  detailed  by 
Jaubert  *  as  follows : 

The  reaction  by  which  the  hydrogen  is  produced  is  carried  out  under  a  pressure 
above  the  vapor  pressure  of  water  at  the  temperature  in  question,  the  larger  part 
of  the  heat  produced  is  localized  and  stored  in  the  reacting  liquid,  and  by  preventing 
the  vaporization  of  this  liquid,  dry  hydrogen  is  obtained,  the  speed  of  manufacture 
is  increased,  and  the  amount  of  liquid  necessary  for  the  reaction  diminished.  The 
pressure  is  produced  automatically  by  working  with  an  autoclave  generator,  in  which 
the  hydrogen  produced  is  allowed  to  accumulate.  The  generator  is  a  revolving 
cylinder,  provided  with  an  autoclave  cover,  a  charging  chamber  which  penetrates 
some  distance  into  the  interior  of  the  cylinder  and  a  blow-off  cock,  so  that  complete 
mixing  of  the  reagents  can  be  prevented  before  the  reaction  is  started  and  to  allow 
the  hydrogen  formed  to  be  drawn  off. 

To  obtain  a  rapid  and  constant  evolution  of  hydrogen  by  the  interaction  of  sili- 
con, aluminium  or  alloys  containing  the  same,  with  an  alkali  hydroxide,  Jaubert 
(French  Patent  454,616,  April  30,  1912)  prepares  an  emulsion  of  a  concentrated 

*  French  Patent  433,400,  Oct.  25,  1910. 


252  THE  HYDROGENATION  OF  OILS 

solution  of  the  latter  with  a  non-saponifiable  oil  or  grease,  such  as  paraffin,  which 
mixture  is  heated  to  100°  C.,  with  the  elements  or  alloys  named,  in  the  form  of  fine 
powder,  water  being  added  as  fast  as  it  is  decomposed,  and  the  frothy  mass  being 
kept  constantly  agitated.* 

Mauricheau-Beaupre  f  adds  to  fine  aluminium  filings  a  small  pro- 
portion of  mercuric  chloride  and  potassium  cyanide,  which  causes  a 
slight  rise  of  temperature  and  produces  a  coarse  powder,  quite  stable 
if  kept  from  moisture.  This  powder  is  treated  with  water  (about 
1  liter  to  a  kilo)  and  the  rise  of  temperature  which  occurs  as  the 
hydrogen  is  evolved  is ,  watched,  and  regulated  if  necessary  by  the 
addition  of  more  water  so  that  the  temperature  does  not  rise  above 
70°  C.  At  this  temperature  1  kilo  of  the  powder  is  completely 
oxidized  in  about  two  hours. 

The  advantages  of  this  method  are  that  the  apparatus  needed  is  of  the  simplest 
description,  and  can  be  made  of  almost  any  materials,  as  the  products  are  perfectly 
neutral;  that  the  gas  produced  is  pure;  and  that  a  very  large  volume  is  yielded  by  a 
small  weight  of  volume  of  the  reagent  (1  kilo  yields  1300  liters,  or  1  cubic  decimeter 
1770  liters).  Pure  aluminium  filings  with  1  to  2  per  cent  of  mercuric  chloride  and 
0.5  to  1  per  cent  of  potassium  cyanide  should  be  used.  (French  Patent  392,725, 
July  27,  1908.)  Aluminium  hydroxide  is  obtained  as  a  by-product. 

Chem.  Fabr.  Griesheim-Elektron  {  recommend  a  preparation  con- 
sisting of  finely-divided  aluminium  (98  parts)  mixed  with  small 
quantities  of  mercuric  oxide  (1  part)  and  caustic  soda  (1  part).  On 
treatment  with  water,  hydrogen  is  evolved  steadily  and  uniformly, 
1  to  1.2  cubic  meters  (calculated  at  0°  C.  and  760  mm.)  being 
obtained  from  1  kilo  of  the  product.  The  mass  can  be  kept  un- 
altered for  a  long  time  if  protected  from  moisture,  and  can  be  easily 
transported,  1  kilo  occupying  a  volume  of  only  0.8  liter.  The  cost 
is  about  forty-five  cents  per  cubic  meter. 

In  the  corresponding  British  Patent  3188,  Feb.  9,  1909,  it  is  stated  that  aluminium 
in  a  divided  form,  such  as  filings,  dust,  chips  or  factory  waste,  is  mixed  with  a  small 
quantity  of  a  compound  of  a  metal  such  as  mercury,  which  is  electro-negative  to 
aluminium,  and  with  a  small  quantity  of  an  alkali  or  acid,  or  a  borate,  phosphate  or 
other  soluble  substance.  The  alkali,  etc.,  serves  to  generate  sufficient  hydrogen  to 
reduce  the  mercury  or  other  compound,  which  then  forms  an  electro-chemical  couple 
with  aluminium  and  decomposes  water  until  the  aluminium  is  used  up. 

According  to  Uyeno,§  78  to  98  parts  by  weight  of  aluminium  are 
melted  in  a  crucible  and  a  mixture  of  15  to  1.5  parts  of  zinc  and  7.0  to 

*  See  also  U.  S.  Patents  to  Jaubert:  943,022,  Dec.  14,  1909;   1,029,064,  June 
11,  1912;   1,037,919,  Sept.  10,  1912;  and  1,040,204,  Oct.  1,  1912. 
t  Compt.  rend.  (1908),  147,  310. 
j  German  Patent  229,162,  Jan.  17,  1909. 
§  British  Patent  11,838,  May  18,  1912. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION     253 

0.5  part  of  tin  are  added  to  the  molten  metal,  after  which  the  alloy 
is  cast  in  the  form  of  a  plate.  For  each  part  of  this  alloy  0.12  to 
0.025  part  of  mercury,  or  a  quantity  of  zinc  or  tin  amalgam  containing 
this  amount  of  mercury,  is  taken  and  amalgamated  with  the  upper 
and  lower  surfaces  of  the  plate  by  rubbing  it  in  with  a  steel  brush. 
The  plate  is  then  heated  to  as  high  a  temperature  as  possible  with- 
out volatilizing  the  mercury,  until  the  alloy  has  become  uniformly 
amalgamated,  whereupon  it  is  ready  for  the  manufacture  of  hydrogen 
by  acting  on  it  with  hot  water. 

When  zinc  dust  is  heated  with  hydrated  lime,  as  previously  stated, 
hydrogen  is  formed  according  to  the  equation, 

Ca02H2  +  Zn  =  ZnO  +  CaO  +  H2. 

On  this  reaction  Majert  and  Richter  *  have  based  a  technical  process 
of  generating  hydrogen,  in  which  they  employ  apparatus  as  shown 
in  Fig.  84.  A  heating  chamber  F  carries  a  series  of  horizontal  tubes 


FIG.  84. 

r,  each  of  which  is  provided  at  one  end  with  a  gas  eduction  pipe  e, 
leading  to  a  water  seal  V,  and  at  the  other  end  with  a  removable  cap. 
Iron  or  carbon  may  be  used  in  place  of  zinc. 

In  the  Lahousse  process  f  coal,  mixed  with  barium  sulfate,  is 
heated  at  a  red  heat  so  as  to  produce  carbon  monoxide  and  barium 
eulfide,  according  to  the  equation, 

BaS04  +  4  C  =  BaS  +  4  CO. 

The  sulfide  of  barium  produced  is  then  heated  to  redness  in  a  current 
of  steam,  with  re-formation  of  barium  sulfate  and  evolution  of 

hydrogen. 

BaS  +  4  H20  =  BaS04  +  4  H2. 

*  Brahmer,  Chemie  de  Case,  101. 

t  French  Patent  361,866,  Oct.  24,  1905. 


254 


THE  HYDROGENATION  OF  OILS 


The  regenerated  barium  sulfate  is  ready  for  use  de  novo.  The 
carbon  monoxide  produced  in  the  first  operation  may  be  employed 
for  heating  the  retorts.  Lahousse  also  states  that  sulfate  and  sul- 
fide  of  strontium  may  be  used  in  place  of  the  corresponding  barium 
compounds.* 

The  Bergius  process.  Steam  acts  on  incandescent  carbon  to  pro- 
duce hydrogen  and  carbon  monoxide.  Below  650°  C.  carbon  dioxide 
instead  of  carbon  monoxide  is  formed  to  some  extent  according  to  the 
reaction, 

C  +  2  H2O  =  CO2  +  2  H2. 

Bergius  has  found  that  this  reaction  occurs  al- 
most exclusively  if  water  at  a  temperature  of 
about  300°  C.  is  allowed  to  act  on  carbon  under 
a  pressure  sufficient  to  keep  the  water  in  a  liquid 
state.  The  addition  of  small  amounts  of  thal- 
lium salts  is  beneficial  as  the  reaction  is  there- 
by promoted  through  catalytic  action.  In  order 


FIG.  85. 


Fin.  86. 


to  work  under  the  high  pressures  necessitated  by  these  consider- 
ations Bergius  has  made  use  of  apparatus  as  shown  in  Figs.  85 
and  86. 

The  successful  closure  of  the  reaction  chamber  was  attained  by  the  use  of  a 
tapered  plug  forced  into  a  seat  having  a  taper  of  different  angle  so  that  the  contact 
becomes  a  line  rather  than  a  surface.  (Bergius,  Die  Anwendung  hoher  Drucke  bei 
Chemischen  Vorgangen,  Halle,  1913,  6.)  A  charge  of  say  100  kilos  coke  and  200 

*  First  Addition,  Oct.  28,  1905,  to  French  Patent  361,866. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION     255 


kilos  water  containing  in  solution  1  kilo  of  thallium  chloride  is  placed  in  a  strong 
iron  vessel  provided  with  a  valve,  and  the  vessel  is  heated  to  340°  C.     (German 
Patent  259,030,   June  24,    1911.)     The 
mixture  of  hydrogen  and  carbon  dioxide 
which  collects  in  the  upper  part  of  the 
vessel  is  blown  off  through  the  valve  at 
intervals  of  half  an  hour,  and  the  carbon 
dioxide  is  absorbed  by  lime. 

Using  iron  instead  of  carbon, 
Bergius  *  has  developed  a  process 
of  making  hydrogen  without  the 
accompanying  formation  of  car- 
bon dioxide,  based  on  the  reaction 
between  iron  or  other  metal  and 
water  at  a  temperature  of  300°  C., 
or  so.f  A  receptacle  as  shown  in 
Fig.  87  is  employed.  This  has  an 

expanded   basal   part   serving   as 

a  reaction   chamber  and  a  long 
tubular  outlet. t 

Iron  and  water  (which  should  contain 
an  electrolyte  such  as  sodium  chloride) 
are  placed  in  the  chamber  and  are  heated 
to  300°  C.  The  pressure  rises  to  100 
atmospheres  or  higher.  Water  condenses 
In  the  tubular  outlet  and  flows  back 
into  the  reaction  zone.  Hydrogen  is 
blown  off  by  means  of  the  valve  in  the 
upper  part.  It  is  stated  that  in  this 
way  hydrogen  can  be  obtained  directly 


FIG.  87. 


*  Bergius  (Zeitsch.  f.  angew.  Chem.  (1913),  517)  states  that  with  his  process 
hydrogen  containing  less  than  1/100  of  a  per  cent  of  impurities  may  be  produced.  In 
apparatus  which  has  been  thoroughly  tested  at  Hanover,  a  vessel  of  a  capacity  of  80 
liters  produced  12  cubic  meters  of  hydrogen  hourly.  Bergius  states  that  the  construc- 
tion of  vessels  of  larger  size  up  to  a  capacity  of  about  one  cubic  meter  offers  no 
difficulty.  In  large  plants  which  are  arranged  for  proper  heat  utilization,  Bergius 
estimates  the  cost  of  hydrogen  at  about  2  cents  per  cubic  meter.  The  advantage 
of  this  process  is  that  very  pure  hydrogen  under  high  pressure  may  be  produced  at 
a  low  cost  and  without  an  expensive  equipment,  enabling  works  requiring  only  a 
small  amount  of  hydrogen  to  produce  this  gas  on  the  spot  at  low  cost.  The  iron 
oxide  formed  by  the  reaction  can  be  reduced  by  heating  with  carbon  at  1000°  C. 
and  is  then  ready  to  be  used  a  second  time. 

t  German  Patent  254,593,  Oct.  24,  1911,  and  German  Patent  262,831,  July  7, 
1912. 

J  Apparatus  fitted  with  an  agitator  and  adapted  for  the  treatment  of  liquids  with 
gas  under  high  pressures  is  described  in  Chem.  Ztg.  (1913),  1288. 


256  THE  HYDROGENATION  OF  OILS 

under  a  pressure  of  more  than  100  atmospheres.  Lower  oxides  of  metals  may  re- 
place the  metals  themselves.  (French  Patent  447,080,  Aug.  9,  1912.)  The  water 
may  contain  neutral  salts,  acids  or  other  conductive  compounds.  The  reaction  is 
also  accelerated  by  the  use  of  a  second  metal,  such  as  copper,  nickel  or  platinum, 
more  electropositive  than  the  principal  metal.* 

*  Badische  Anilin  und  Soda  Fabrik.,  French  Patent  441,695,  March  23,  1912. 
Operations  in  which  hydrogen,  or  gases  containing  it,  are  employed  under  pressure 
and  at  a  high  temperature  can  be  carried  out  in  vessels,  provided  with  special 
strengthening  appliances,  although  the  wall  of  the  interior  vessel  in  which  the  reac- 
tion takes  place  is  composed  of  some  material,  such  as  iron  free  from  carbon  or 
nickel,  which  is  incapable  of  offering  by  itself  sufficient  mechanical  resistance  to 
the  conditions  imposed  by  the  process,  but  chemically  is  as  resistant  as  possible  to 
hydrogen.  (See  also  U.  S.  Patent  1,077,034,  Oct.  28,  1913;  and  1,075,085,  Oct.  7, 
1913.) 

Hydrogen  under  pressure  may  be  used  in  conjunction  with  vessels  constructed 
of  steel  alloys  at  temperatures  considerably  above  450°  C.  when  these  alloys  con- 
tain certain  proportions  of  chromium,  vanadium,  tungsten,  molybdenum  or  the 
like.  Suitable  alloys  contain  (1)  tungsten  18  and  chromium  3  per  cent,  and 
(2)  chromium  2.9  and  carbon  0.2  per  cent.  Alloys  containing  too  high  a  percentage 
of  nickel  should  be  avoided.  (J.  S.  C.  I.  (1913),  1010;  Badische  Anilin  und  Soda 
Fabrik.,  British  Patent  29,260  and  13,258,  Dec.  19,  1912,  and  June  7,  1913.) 


CHAPTER  XIX 
HYDROGEN   BY  THE   ELECTROLYSIS   OF  WATER 

The  production  of  hydrogen  and  oxygen  by  the  electrolysis  of 
water,  though  one  of  the  oldest  electrochemical  experiments,  and 
proposed  in  a  large  number  of  patents,  in  the  past  has  been  carried 
out  industrially  only  to  a  limited  extent.  There  was  considerable 
difficulty  in  developing  the  laboratory  apparatus  so  that  it  would 
operate  successfully  in  practice,  one  of  the  hardest  conditions  to  meet 
being  the  necessity  of  absolute  safety  of  operation,  and  this  required 
the  exclusion  of  every  possibility  of  the  formation  of  an  explosive  gas 
mixture.  Another  difficult  matter  was  the  requirement  of  providing  a 
material  for  the  electrodes,  which  was  not  at  all  or  only  slightly  attacked 
by  the  electrolyte,  and  the  necessity  of  constructing  apparatus  with 
a  small  internal  resistance.* 

These  problems  appear  now  to  have  been  worked  out  satisfactorily 
so  that  large  scale  electrolysis  of  water  is  on  a  solid  industrial  basis. 
The  principal  processes  or  systems  used  in  practice  include  those 
of  the  International  Oxygen  Co.,  Garuti,  Schoop,  Siemens-Halske, 
Schmidt,  Schuckert  and  Burdett.f 

*  The  Electrolysis  of  Water,  Richards  and  Landis,  Trans.  Am.  Electrochem. 
Soc.,  Ill,  104,  and  IV,  112,  is  concerned  largely  with  the  theory  of  the  subject,  while 
a  paper  by  Richards  bearing  the  same  title,  appearing  in  the  Journal  of  the  Franklin 
Institute,  1905,  377,  treats  of  practical  developments  in  hydrogen  and  oxygen  gener- 
ation. 

t  In  the  electrolysis  of  water  there  are  certain  constants  whose  values  are  the 
same  under  all  conditions  of  operation  within  certain  limits.  The  first  constant 
is  the  amount  of  hydrogen  liberated  per  ampere  hour  of  current  passed  through  the 
cell  generator;  the  figure  is  0.03738  gram  or  0.014825  cubic  foot  of  hydrogen  gas 
measured  at  0  degree  and  760  mm.  pressure.  Thus,  at  400  amperes,  which  is  the 
customary  operating  amperage  for  most  cell  generators,  the  production  will  be  5.93 
cubic  feet  of  hydrogen  and  2.96  cubic  feet  of  oxygen  (at  0  degree  and  760  mm.  pres- 
sure) per  hour.  At  20  degrees  and  760  mm.  pressure  the  output  will  be  6.36  cubic 
feet  of  hydrogen  and  3.16  cubic  feet  of  oxygen  per  hour  per  cell  generator.  The 
second  constant  is  the  minimum  voltage  that  will  force  the  current  through  the  cell 
generators.  For  a  solution  of  sodium  hydroxide  in  water  the  minimum  voltage  is 
1.69  volts,  for  potassium  hydroxide  1.67  volts;  this,  then,  is  the  lowest  voltage  at 
which  decomposition  of  water,  or  electrolysis,  takes  place.  In  order  to  produce 
gas  with  current  at  this  voltage,  the  cell  generator  would  have  to  be  constructed 
in  such  a  manner  as  to  do  away  with  all  internal  electrical  resistance  which  is  obvi- 
ously impossible  and  so  the  operative  or  practical  voltage  is  higher  than  the  theoret- 
ical. With  a  current  of  400  amperes  the  voltage  will  vary  from  1.9  to  4,  depending 

257 


258  THE  HYDROGENATION  OF  OILS 

D'Arsonval,  in  1885,  was  perhaps  the  first  to  install  a  plant  for 
furnishing  oxygen  electrically  in  the  laboratory.  He  used  30  per 
cent  caustic  soda  solution  as  electrolyte,  cylindrical  sheet-iron  elec- 
trodes, a  current  density  of  two  amperes  per  square  decimeter,  and 
enclosed  the  anode  in  a  woolen  bag,  to  serve  as  a  diaphragm.  Only 
the  oxygen  was  saved.  The  apparatus  used  sixty  amperes,  furnished 
some  100  to  150  liters  of  oxygen  daily,  and  was  in  use  several  years. 

Latchinoff  used  an  asbestos  cloth  partition,  ten  per  cent  caustic 
soda  solution,  iron  electrodes,  3.5  amperes  per  square  decimeter 
and  2.5  volts  working  tension;  or  with  a  five  to  fifteen  per  cent  sul- 
furic  acid  solution  he  used  lead  anodes  and  carbon  cathodes.  In 
his  first  apparatus,  Figs.  88  and  89,  the  units  were  all  in  parallel,  but 
afterwards  he  used  series  electrodes,  the  one  side  of  an  electrode 
acting  as  an  anode  and  the  other  as  a  cathode;  a  series  of  forty  was 

on  the  type  of  cell  generator.  With  the  first  constant  given  the  amount  of  hydrogen 
produced  per  400  amperes  per  hour  and  the  minimum  or  theoretical  voltage  given 
it  is  a  simple  matter  to  determine  the  yield  of  gas  per  kilowatt-hour  of  electricity 
used.  The  theoretical  efficiency  will  be  400  amperes  X  1.69  volts  or  0.676  kilowatt- 
hour  to  produce  6.36  cubic  feet  of  hydrogen.  The  theoretical  yield  per  kilowatt- 
hour  per  cell  generator  will  be  9.408  cubic  feet  of  hydrogen.  In  practice  the  yield 
is  from  4.5  to  8.25  cubic  feet  of  hydrogen  per  kilowatt-hour. 

In  general,  electrolytic  plants  consist  of  the  following  important  parts,  cell  gener- 
ators for  producing  the  gases,  a  motor-generator  set  to  deliver  a  direct  current  at 
the  proper  potential  or  voltage,  gasometers  and  storage  tanks  for  storing  the  gas 
as  it  is  generated  and  compressors  and  compressor  motors  for  raising  the  pressure 
of  the  gas  to  the  required  point.  Stripped  of  everything  but  essentials  the  compo- 
nent parts  of  all  cell  generators  are:  a  container  tank  for  holding  the  solution;  one 
or  more  positive  electrodes,  one  or  more  negative  electrodes,  immersed  in  the  solu- 
tion; means  for  separating  the  electrodes  to  prevent  mixture  of  gas  and  means  for 
separately  collecting  the  gas  as  it  is  generated.  The  separating  medium  is  usually 
a  diaphragm  and  may  be  of  metal,  earthenware  or  cloth.  The  diaphragm  may  be 
a  conductor  or  non-conductor  of  electricity  and  if  of  conductive  material  it  should 
be  insulated  from  the  electrodes.  The  effect  of  the  diaphragm  is  to  divide  the 
generator  into  two  or  more  partitions,  and  the  gases  as  generated  will  rise  to  the  top 
of  the  partition,  there  to  be  drawn  off  by  means  of  pipes  which  lead  to  header  pipes 
connecting  a  line  of  cell  generators,  each  gas,  of  course,  being  drawn  off  by  means 
of  separate  pipe  lines.  The  header  pipes  in  turn  are  connected  to  a  main  gas  line 
which  leads  the  gases  to  their  respective  gasometers.  From  the  gasometers  the 
gas  is  drawn  off  by  means  of  compressors  and  compressed  into  storage  tanks  for  use. 

The  majority  of  installations  require  a  motor-generator  set  to  obtain  the  required 
voltage  for  operating.  The  current  must  be  direct.  The  motor-generator  set 
should  be  heavily  built  in  order  to  operate  on  a  twenty-four  hour  load.  The  com- 
pressors employed  are  specially  adapted  for  handling  these  gases.  The  size  and 
character  of  the  gasometers  used,  of  course,  depends  on  the  size  of  the  installation. 

Below  is  given  a  typical  operating  cost  of  an  electrolytic  plant  consisting  of 
100  cell  generators  with  a  production  capacity  of  632  cubic  feet  of  hydrogen  and  316 
cubic  feet  of  oxygen  in  one  hour  and  15,168  cubic  feet  of  hydrogen  and  7584  cubic 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 
7, 


259 


a; 


FIG.  88. 


FIG.  89. 


feet  of  oxygen  in  24  hours.     The  yearly  production,  300  days  24  hours  per  day,  is 
4,550,400  cubic  feet  of  hydrogen  and  2,275,200  cubic  feet  of  oxygen. 

Each  cell  generator  requires  about  2  volts  at  400  amperes  equivalent  to  800  watts 
or  0.8  kilowatt-hour. 

100  cells  X  0.8  K.W.H.  X  24  hours  X  300  days  =  576,000  K.W.H.  yearly  plus 
25  per  cent  for  loss  through  motor-generator  set  =  720,000  K.W.H.  yearly. 
Hydrogen  compression  requires  4  K.W.H.  per  hour. 
4  K.W.H.  X  24  hours  X  300  days  =  28,800  K.W.H.  yearly. 

(Compression  to  300  pounds  per  square  inch.) 
Oxygen  compression  requires  12  K.W.H.  per  hour. 
12  K.W.H.  X  24  hours  X  300  days  =  86,400  K.W.H.  yearly. 

(Compression  to  1800  pounds  per  square  inch.) 
Current  consumption  yearly: 

Cell  generators 720,000 

Hydrogen  compression 28,800 

Oxygen  compression 86,400 

Total 835,200 

Fixed  charges: 

Depreciation,  maintenance,  yearly $3000 . 00 

Interest  on  investment 1500.00 

Labor: 

300  days,  24  hours,  at  30  cents  per  hour $2160.00 

With  current  at  a  price  of  say  1  cent  per  kw.-hour,  which  although  a  low  rate  is 
not  excessively  low  for  this  class  of  service,  the  total  operating  cost  will  be  $15,012.00 
per  year. 

The  demand  for  oxygen  in  metal  working  lines  is  at  present  so  great  and  so  poorly 
met  that  in  the  majority  of  cases  the  oxygen  produced  by  an  electrolytic  plant  may 
be  disposed  of  under  contract  at  such  terms  as  will  result  in  the  hydrogen  being 
produced  at  a  relatively  low  cost. 


260 


THE  HYDROGENATION  OF  OILS 


used  on  a  normal  lighting  circuit,  with  current  density  of  ten  amperes 
per  square  decimeter,  and  parchment  partitions  between  the  electrodes 
to  separate  the  gases.  Latchinoff  was  also  the  first  to  carry  out  the 
decomposition  under  pressure,  using  a  strong  iron  vessel  as  elec- 
trolyzer,  and  by  an  ingenious  system  of  floating  valves  keeping  the 
pressure  of  the  two  gases  equal  in  the  apparatus.  Fig.  90  shows  this 
apparatus,  the  action  of  which  will  be  evident  from  a  short  inspec- 
tion. 

Renard's  apparatus  for  the  generation  of  hydrogen  is  shown  in 
Fig.  91.     The  container  is  made  of  cast  iron  and  serves  as  the  nega- 


FIG.  91. 


tive  electrode.  The  cylinder  C  of  asbestos  material  encloses  the 
positive  electrode  which  is  cylindrical  in  shape  and  is  made  either  of 
iron  or  nickel.  Through  the  bottom  of  the  diaphragm  cylinder  the 
U-tube  R  establishes  communication  between  the  inner  and  outer 
vessels.  The  electrolyte  is  a  solution  made  by  dissolving  15  parts 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         261 


m 


FIG.  92. 


FIG.  93. 


FIG.  94. 


262 


THE   HYDROGENATION  OF  OILS 


1 


of  caustic  soda  in  100  parts  of  water.  Before  the  gases  are  passed 
to  the  gas  holder  they  are  led  through  the  pressure  equalizer  marked 
H  and  0.  With  a  current  of  25  amperes  at  3.5  volts  a  yield  of  12 
liters  of  hydrogen  and  6  liters  of  oxygen  per  hour  is  obtained. 

A  form  of  construction  of  the 
Renard  *  type  is  shown  in  Fig.  92 
and  also  in  Fig.  93. 

The  multiple  cell  of  Schmidt  f 
looks  somewhat  like  a  filter  press, 
Fig.  94,  and  consists  essentially  of 
bipolar,  iron  electrodes,  connected 
in  series.  Each  frame  in  the  press 
contains  an  iron  electrode,  which 
acts  as  a  double-pole  (bipolar)  elec- 
trode, sheets  of  asbestos  cloth  held 
between  the  frames  acting  as  par- 
titions, reinforced  with  rubber  on 
the  edges  for  making  tight  joints. 
The  electrolyte  is  a  ten  per  cent 
solution  of  potassium  carbonate, 
filled  into  the  apparatus  through  the 
standpipe  on  the  right,  which  com- 
municates with  all  the  compartments 
through  holes  in  the  frames  similar 
to  the  usual  filter-press  construction. 
The  gases  evolved  escape  by  similar 
passages  into  the  cylinders  on  the  left 
end,  where  they  separate  from  the 
electrolyte  and  pass  upwards,  while 

the  electrolyte,  dragged  by  the  gas  bubbles,  flows  downwards  back 
into  the  apparatus,  thus  maintaining  an  efficient  circulation.  With 
forty  plates  about  2.5  volts  are  absorbed  in  each  cell,  using  a  current 
density  of  about  two  amperes  per  square  decimeter. { 

The  apparatus  is  shown  in  detail  in  Fig.  95.  A  110- volt  direct- 
current  lighting  circuit  may  be  employed  for  the  operation  of  a  series 
type  apparatus  composed  of  the  requisite  number  of  cells.  The  press 

*  Delmard,  German  Patent  58,282,  Nov.  23,  1890. 

t  German  Patent  111,131,  June  13,  1899. 

|  A  multiple-cell  generator  of  the  filter  press  type  is  manufactured  by  Shriver  & 
Co.,  Harrison,  N.  J. 

A  filter-press  type  of  hydrogen  generator  having  an  output  of  16  cu.  m.  of  hydrogen 
per  hour  is  made  by  Maschinenfabrik  Surth,  G.m.b.h.  Siirth  am  Rhein  bei  Koln. 


FIG.  95. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER          263 


-= 

I 


264 


THE  HYDROGENATION  OF  OILS 


has  to  be  taken  apart  and  cleaned  every  six  weeks  and  the  asbestos 
diaphragms  have  to  be  renewed  from  time  to  time. 


A 


I 
I 

I) 


FIG.  98. 


A 


-a- 


Jl  //////7/////////////////y//////////////////////////./7/ 
FIG.  97. 


FIG.  99. 


Schoop,  in  1900,  devised  an  apparatus  with  non-conducting  and 
non-porous  partitions,  which  has  gone  into  considerable  commercial 
use.  Fig.  97  shows  the  section  of  the  apparatus,  where  aa  are  the 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         265 


tubular  electrodes  of  sheet  hard  lead,  enclosed  by  glass  or  clay  sus- 
pended tubes  c,  which  are  perforated  at  their  lower  end;  the  electrode 
surface  is  further  increased  by  fine  hard  lead  or  iron  wires  hung  inside 
the  tubular  electrodes,  the  latter  being  perforated  above  the  level 
of  the  electrolyte  in  order  to  let  the  internally-generated  gas  escape. 
Each  cylinder  contains  two  anodes  and  two  cathodes.  When  alkaline 
electrolytes  are  used  and  iron  electrodes,  the  working  voltage  is  2.25; 
when  sulfuric  acid  of  density  1.235  is  used,  with  hard-lead  electrodes, 
the  working  voltage  is  3.6  to  3.9.  Fig.  98  shows  a  single  electrode  and 
Fig.  99  an  installation  of  the  Schoop  system.* 


-l>    4  a 


-k   -fa 


FIG.  100. 


FIG.  101. 


C 

K 

K      1 

FIG.  102. 

Garuti,  in  1892,  introduced  a  new  electrolytic  principle  into  these 
apparatus  for  the  decomposition  of  water.  He  used  a  nearly  com- 
plete metallic  partition  between  the  electrodes,  and  avoided  the  evolu- 
tion of  gases  on  this  partition  by  keeping  the  working  voltage  between 
the  electrodes  below  three  volts.  A  metallic  partition  can  only  act  as 
an  intermediate  or  bipolar  electrode  by  virtue  of  the  current  entering 
and  leaving  it;  but  this  would  make  two  decompositions  between 

*  Schoop  (Zeits.  Elcktrotechn.  Wien  (1900),  18,  441)  discusses  the  difficulties 
met  with  in  the  construction  of  a  suitable  apparatus  for  the  technical  electrolytic 
manufacture  of  hydrogen  and  oxygen,  and  gives  a  description  of  patents  dealing 
with  this  subject.  In  the  Schoop  apparatus  it  is  claimed  that  1.5  cubic  meters 
of  hydrogen  and  oxygen  are  produced  per  11  horse-power  hours.  Richards  (Jour. 
Franklin  Inst.  (1905),  390)  notes  that  the  output  is  given  as  68  liters  of  oxygen  and 
136  liters  of  hydrogen  per  electrical  horse-power  hour.  A  description  of  the  Schoop 
system  is  given  in  the  Centralblatt  f.  Accum.,  Feb.  15,  1903.  It  is  stated  that  the 
length  of  the  tubes  is  chosen  according  to  the  pressure  under  which  the  gases  are 
wanted.  The  following  results  were  obtained  with  the  Schoop  apparatus  during 
one  year:  One  electric  horse-power  hour  gives  97.5  liters  of  hydrogen  and  48.75  oxy- 
gen (probably  under  atmospheric  pressure);  i.e.,  for  one  cubic  meter  of  mixed  gas 
6.8  horse-power  hours  are  required;  with  warm  acid  (sulfuric  acid  of  1.23  specific 
gravity  being  always  used)  this  value  is  reduced  to  6.2  horse-power  hours;  if  the 
price  of  one  horse-power  is  1  cent,  the  cost  of  the  production  of  one  cubic  meter  of 
mixed  gases  is  4.2  to  4.8  cents.  The  purity  of  the  oxygen  is  99  per  cent,  that  of  the 
hydrogen  97.5  to  98  per  cent. 


266 


THE  HYDROGENATION  OF  OILS 


the  original  electrodes,  necessitating  an  absorption  of  2  X  1.5  =  3 
volts  in  decomposition.  As  long  as  the  working  voltage  is  kept 
below  3,  the  partition  must  act  merely  as  a  partition,  the  same  as  a 
non-conducting  partition.  Reference  to  Figs.  100,  101  and  102  will 
make  this  entirely  clear.  If  2  electrodes  are  placed  in  a  vessel  (Fig.  100) 

containing  acidulated  water  and 
are  separated  by  a  sheet  of  metal 
c  (Fig.  101),  two  separate  decom- 
position chambers  result  and  the 
sheet  metal  serves  as  a  bipolar 
electrode,  so  that  the  side  towards 
the  anode  evolves  hydrogen  and 
that  towards  the  cathode,  oxygen. 
Since  the  1.5  volts  are  required 
for  the  decomposition  of  water, 
the  cells  M  and  N  will  require  3 
volts.  If  the  diaphragm  is  raised 
somewhat  so  the  chambers  M  and 
N  are  in  communication  (Fig.  102) 
the  evolution  of  gas  will  take  place 
only  on  the  terminal  electrodes 
and  not  on  the  intermediate  con- 
ducting septum.  The  latter  be- 
comes a  bipolar  electrode  only 
when  the  electromotive  force  ex- 
ceeds 3  volts.  The  advantage 
gained  by  the  Garuti  process  is 
in  the  simplicity  and  economy  of 
making  the  partitions  of  sheet 
metal  instead  of  burnt  clay,  rubber,  glass,  etc. 

Garuti  devised  many  modifications  in  the  details  of  his  cells,  of 
which  Fig.  103  may  represent  the  most  recent.  The  original  forms 
made  of  sheet  lead  (using  dilute  sulfuric  acid  electrolyte)  got  out 
of  shape  too  easily,  and  were  replaced  by  sheet-iron  apparatus,  using 
caustic  soda  solution.  The  electrodes  are  only  twelve  millimeters  from 
each  other,  and  separated  by  a  sheet-iron  partition  with  small  per- 
forations in  it,  the  latter  allowing  free  passage  of  current  but  being 
too  small  to  allow  any  gas  bubbles  to  pass.  The  alternate  compart- 
ments are  connected  with  oxygen  and  hydrogen  mains,  in  which  are 
enlargements  for  collection  of  spray  and  moisture,  which  runs  back 
into  the  cell.  Current  densities  of  two  to  three  amperes  per  square 
decimeter  are  possible  with  a  working  voltage  between  2.45  and  3, 


FIG.  103. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         267 

using  caustic  soda  solution  of  21°  Be.     The  cell  shown  in  Fig.  104  is 
intended  to  take  400  amperes,  and  to  require  one  kilowatt  of  power. 
The  Garuti  type  Cll  generator  consists  of  45  separate  compart- 


FIG.  104. 

ments  made  of  16-gauge  sheet  iron  welded  together  to  form  a  single 
unit.*  The  sides  of  the  compartments  are  used  as  diaphragms  and  are 
usually  perforated  (Fig.  105)  to  allow  circulation  of  the  electrolyte  but 


FIG.  105. 


FIG.  106. 


Perforated  compartment  walls  of  the  Garuti  generator. 

*  In  1892  Garuti  took  out  a  patent  (British  Patent  16,588,  April  25,  1892)  de- 
scribing an  apparatus  consisting  of  a  container  having  an  inverted  leaden  case  with 
partitions  of  sheet  lead  soldered  together  so  as  to  form  a  case  divided  into  parallel 
cells  open  only  to  the  water  at  the  bottom.  The  partitions  of  the  cells  separate  the 
anodes  and  cathodes  which  are  placed  alternately  and  are  insulated  in  the  cells  by 
means  of  combs  made  of  suitable  material.  In  1896  Garuti  and  Pompili  (British 
Patent  23,663,  Oct.  24,  1896)  described  an  improvement  on  the  former  patent, 
involving  the  perforation  of  the  diaphragms  in  their  lower  part  by  small  holes  as 
near  as  possible  to  each  other.  See  also  U.  S.  Patents  to  Garuti  534,259,  Feb.  19, 
1895,  and  Garuti  and  Pompili  629,070,  July  18,  1899. 


268 


THE  HYDROGENATION  OF  OILS 


not  the  gas.     The  perforations  extend  lengthwise  along  the  lower 
edge  of  each  compartment  wall  3  inches  from  the  bottom,  forming  a 
perforate  strip  2|  inches  wide.     An  electrode 
is  placed  in  each  compartment  and  the  elec- 
trodes are  alternately  positive  and  negative.  All 
like  electrodes  are  connected  together.     Each 
compartment  is  f  inch  in  width  and  30  inches 
long.     The  electrodes  are  insulated  from  the 
compartments  and  are  prevented  from  coming 
in  contact  with  the  walls  by  means  of  small 
porcelain  insulators.     The  gas  from  all  of  the 
FIG.  107.    Compartments  hydrogen-producing  compartments  is  collected 
of  the  Garuti  generator. 


and  is  led  through  a  water  seal  and  to  a  header  pipe  and  then  to  a 
gasometer.  The  oxygen  gas  is  handled  in  a  like  manner.  The  cells 
as  well  as  the  container  tanks  and  pipe  lines  are  insulated  from  the 
ground.  The  pipe  from  the  cell  to  the  header  pipe  is  insulated  from 
the  latter  by  means  of  a  sleeve  of  rubber  and  glass.* 

Siemens  Bros.  &  Co.  and  Obach  devised  the  apparatus  shown  in 
Fig.  112,  the  principle  being  similar  to  that  of  the  Garuti.  The  cast- 
iron  vessel  a  is  surrounded  by  heat-retaining  material,  in  order  that 
the  temperature  of  the  cell  may  be  automatically  raised  and  thus  its 
running  resistance  lowered.  A  cylindrical  iron  anode  /  is  separated 
from  the  encircling  cathode  g  by  a  cylinder  of  wire  netting  c,  held 
in  place  by  the  porcelain  block  k.  The  electrolyte  is  dilute  caustic 
soda;  the  gases  escape  above  from  the  spaces  n  and  m.  The  whole 

*  When  the  Garuti  cell  is  first  installed  the  efficiency  will  often  be  as  high  as 
6  cubic  feet  or  so  of  hydrogen  per  kw.-hour,  but  the  depreciation  is  said  to  be  perhaps 
more  rapid  than  in  some  other  types  of  generators  and  in  time  the  hydrogen  output 
may  drop  to  about  5  cubic  feet.  Thus  under  the  normal  operating  amperage  of 
350  or  400,  from  2£  to  3  volts  per  cell  will  be  required.  The  rather  rapid  deprecia- 
tion of  the  generator  is  said  to  have  held  back  its  use  to  some  extent.  Owing  to 
the  lightness  of  the  materials  employed  and  also  possibly  because  of  insufficient 
electrode  surface,  the  anode  is  liable  to  be  attacked  and  eventually  worn  away.  The 
minute  particles  of  iron  or  iron  compounds  formed  are  said  to  have  a  tendency  to 
be  deposited  on  the  cathode.  The  insulators,  employed  to  prevent  the  contact  of 
electrode  with  the  compartment  wall,  form  a  convenient  place  of  deposit  for  the 
iron  particles  with  possible  danger  of  causing  a  short  circuit  between  the  electrode 
and  the  compartment  walls.  If  one  compartment  is  short  circuited  the  entire  cell 
becomes  "shorted"  and  this  short  circuit  will  cause  the  generation  of  mixed  gas. 
The  entire  cell  should  be  dismantled  about  once  a  year  and  cleaned  with  either  a 
stream  of  water  or  by  means  of  a  sand  blast. 

The  American  Oxhydric  Company,  Milwaukee,  Wis.,  have  had  generators  of 
the  Garuti  type  in  operation  for  several  years. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER          269 


FIG.  108.     Garuti  generator. 


FIG.  109.     Battery  of  Garuti  generators. 


270 


THE  HYDROGENATION  OF  OILS 


FIG.  110.    One  form  of  the  Garuti  generator. 


rv         TT 


FIG.  111.     A  modified  form  of  the  Garuti  generator. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         271 


apparatus  is  set  on  insulating  porcelain  feet.  The  normal  type  of 
apparatus  is  built  to  take  750  amperes  at  3  volts  drop  of  potential,  and 
furnishing  eleven  cubic  meters  of  oxygen  and  twenty-two  cubic 
meters  of  hydrogen  per  twenty-four 
hours,  using  up  162  kilowatt-hours.* 
Fiersot  describes  f  an  apparatus  of 
Siemens  and  Halske  for  the  electrol- 
ysis of  water  in  which  a  10  per  cent 


FIG.  112.  FIG.  113.      Plan  and  elevation  of 

Siemens  Bros,  and  Obach  generator. 

solution  of  potassium  carbonate  is  used  as  electrolyte.  One  hundred 
and  thirty-four  grams  of  water  are  decomposed  per  kilowatt-hour. 
By  heating  the  electrolyte  the  output  may  be  increased  by  8  per  cent. 
The  electrolytic  oxygen  thus  produced  is  on  the  average  97  per  cent 
pure,  while  the  hydrogen  contains  one  per  cent  of  oxygen. 

Another  form  of  metallic   diaphragm  cell  has   been   devised   by 
Fischer,  Luening  and  Collins. t      The  generator  consists  of  a  tank 

*  Jour.  Franklin  Inst.  (1905),  392. 
t  Electrochemical  Ind.  (1904),  28. 
J  U.  S.  Patent  1,004,249,  Sept.  26,  1911. 


272 


THE  HYDROGENATION  OF  OILS 


containing  an  electrolyte  in  which  an  indifferent  number  of  indepen- 
dent, preferably  oblong,  metallic  cases  are  submerged.    An  illustration 
A  of  the  case  is  shown  in  Fig.  114.    The 

A  case  is   open  at  the  bottom  and  is 

HI  JSi^^i  divided  into  a  pair  of  cells  by  a 
metallic  diaphragm.  Electrical  con- 
nections to  the  anode  and  cathode 
and  exit  pipes  situated  on  the  upper 
side  of  the  case  are  provided  for  the 
removal  of  the  gases. 

The  apparatus  of  the  Schuckert  sys- 
tem *  is  constructed,  with  the  excep- 
tion of  the  copper  feed  wires  and  the 
insulating  material,  entirely  of  iron. 
The  cell  proper  of  a  unit  designed  to 
accommodate  600  amperes  consists  of 
a  cast-iron  trough  (Fig.  115),  approx- 
imately twenty-six  inches  long  by 
eighteen  wide  and  fourteen  deep,  re- 
quiring, when  in  operation,  about  50  liters  of  electrolyte.  In  this  trough 
are  placed  the  iron  electrodes.  These  are  separated  by  strips  of  a  good 
insulating  material,  extending  from  the  top  downward  about  three- 


FIG.  114. 


FIG.  115.    Schuckert  cell 

fourths  the  depth  of  the  cell.  Between  these  separating  plates  and 
enclosing  the  electrodes  are  suspended  iron  bells,  which  collect  and 
carry  off  the  gas  there  generated.  The  electrolyte  is  usually  a  20  per 

*  Electrochem.  Ind.  (1903),  579. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         273 

cent  aqueous  solution  of  pure  sodium  hydrate,  although  a  15  per  cent 
solution  may  be  used.  The  concentration  is  maintained  by  supplying 
to  the  cells  an  amount  of  distilled  water  equal  to  that  decomposed  and 
carried  away  mechanically  by  the  gas.  The  loss  of  sodium  hydrate 


FIG.  116.     Longitudinal  section  of  Schuckert  cell. 

is  inappreciable  and  may  be  entirely  eliminated  if  the  first  wash  water 
be  used  as  feed  water  for  the  cells.  The  units  may  be  connected 
either  in  series  or  parallel  with  a  drop  of  potential  between  electrodes 
of  from  two  and  one-half  and  three  volts.  The  apparatus  is  operated 


FIG.  117.      Cross  section  of  Schuckert  cell. 


most  economically  at  a  temperature  of  70°  C.  When  the  cells  are 
protected  from  radiation,  as  can  be  done,  for  example,  by  placing 
them  on  wooden  boxes  and  packing  them  in  one  or  two  inches  of 
sand,  the  heating  effect  of  the  passing  current  is  sufficient.* 

*  The  Elektrizitats-A-G.  Vorm.  Schuckert  &  Co.  have  taken  out  German 
Patent  231,545,  Aug.  13,  1910,  for  the  addition  of  soaps  or  soap-forming  substances, 
preferably  emulsified  soaps,  and  of  ferric  oxide  to  the  alkaline  electrolyte  employed. 


274 


THE   HYDROGENATION  OF  OILS 


FIG.  118. 


FIG.  119. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         275 

The  standard  types  of  apparatus  are  designed  to  take  from  100  to  1000  amperes, 
and  to  furnish  gas  at  a  pressure  equal  to  a  water  column  of  70  to  80  mm.  For 
special  purposes  a  cell  delivering  gas  sustaining  a  water  column  of  760  mm.  may  be 
secured.  The  production  of  normal  types  of  apparatus  is  about  150  liters  of  hydrogen 
and  75  liters  of  oxygen  per  kilowatt-hour  when  measured  over  water  at  atmospheric 
pressure,  and  at  20°  C.  The  attention  required  for  a  plant  of  this  kind  consists 
simply  in  supplying  the  requisite  amount  of  water  to  maintain  the  concentration 
constant.  When  in  continuous  operation  the  positive  electrode,  which  is  made  up 
of  a  sheet  iron  plate  two  millimeters  thick,  should  be  replaced  at  the  end  of  each 
year.* 

Fig.  118  shows  the  interior  of  a  plant  furnishing  1200  cubic  meters 
hydrogen  daily.  Fig.  119  shows  the  exterior  of  this  plant.  An  equip- 
ment for  an  hourly  production  of  4  cubic  meters  hydrogen  is  shown 
in  Fig.  120.  Fig.  121  is  a  compression  room  for  charging  cylinders 
with  oxygen  at  150  atmospheres  pressure. 


FIG.  120. 


A  modified  form  of  the  Schuckert  cell,  as  shown  in  Figs.  122  and  123,  comprises  a 
container  tank,  constructed  of  welded  sheet  iron  and  a  number  of  positive  and  nega- 
tive electrodes  immersed  in  the  solution.  Eight  separate  bell  castings  are  employed 
to  house  the  electrodes  and  collect  the  gas  as  it  is  generated.  These  bell  castings 
are  made  of  a  close-texture  gray  iron  and  are  suspended  from  the  top  of  the  container 
tank  by  means  of  U-shaped  steel  supports.  The  container  tank  and  the  bell  castings 


See  Sci.  Am.  Suppl.  (1913),  363. 


276 


THE  HYDROGENATION  OF  OILS 


play  no  part  in  the  operation  of  the  generator  and  are  insulated  from  the  electrodes 
and  all  current-carrying  metal.  The  electrodes  are  made  of  steel  plates  to  each  of 
which  are  welded  two  steel  rods,  both  rods  serving  as  terminals  as  well  as  supports 
for  the  electrode,  holding  it  in  position  within  the  bell  casting.  The  electrodes  are 
alternately  positive  and  negative.  All  of  the  positive  electrodes  are  connected 
together  by  means  of  bus  bars  across  the  top  of  the  tank  and  are  led  to  a  common 
terminal.  The  negative  electrodes  likewise  are  connected  together  and  led  to  a 
common  terminal.  Each  bell  casting  is  tapped  for  an  eduction  pipe  to  draw  off 
the  gas  as  generated.  The  four  hydrogen  pipes  are  connected  together  as  shown 
and  are  led  to  the  hydrogen  pipe  line  connecting  a  battery  of  generators.  The 
oxygen  pipes  are  connected  likewise.  The  electrolyte  fills  the  container  and  owing 
to  its  height  above  the  electrodes  the  gas  is  generated  under  an  appreciable  pressure 
amounting  to  approximately  one  pound  per  square  inch. 


FIG.  121. 


The  novelty  that  distinguishes  the  Schuckert  cell  from  the  majority  of  other  gener- 
ators is  the  absence  of  any  diaphragm  in  the  construction.  While  a  diaphragm  is 
actually  not  used,  still  the  sides  of  the  bell  castings  act  in  the  capacity  of  a  diaphragm 
to  prevent  the  mixing  of  the  gases. 

The  working  efficiency  of  the  Schuckert  cell  under  normal  conditions  of  temper- 
ature is  said  to  average  from  4.5  to  5.5  cubic  feet  of  hydrogen  per  kilowatt-hour  of 
electricity  passed  through  it.  Or,  in  other  words,  the  voltage  required  to  force  400 
to  600  amperes  through  each  cell  will  vary  from  2.9  to  3.5  according  to  the  condition 
of  the  plant.  The  Schuckert  generator  was  one  of  the  earliest  placed  on  the  market 
and  at  the  present  time  three  plants  of  this  type  are  reported  in  use  in  the  United 
States.  Too  high  an  amperage  results  in  so  rapid  an  evolution  of  gas  that  there  is 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


277 


-2--7T 


FIG.  122. 


FIG. 


a  tendency  under  these  conditions 
for  the  gas  in  one  chamber  to  be 
forced  down  and  under  the  wall 
of  the  next  partition  which,  of 
course,  will  result  in  mixed  gas  or 
the  escape  of  gas  into  the  gen- 
erator room. 

Another  difficulty  said  to  be 
met  with  in  operating  under  high 
amperage  is  the  wearing  away 
of  the  anode,  charging  the  elec- 
trolyte with  small  particles  of 
iron  compounds  which  show  a 
tendency  to  be  attracted  to  the 
cathode  and  gradually  form  a 
deposit.  These  accretions  have 
been  known  to  build  across  the 
space  between  the  electrode  and 
the  bell  castings  causing  short- 
circuiting  and  permitting  the  bell 
castings  to  become  charged,  with 
consequent  evolution  of  gas  on  its 
outer  side  and  the  escape  of  gas 
into  the  generating  room.* 

Details  of  construction  of  an  electrolytic  apparatus  for  the  production  of  hydro- 

*  The  Schuckert  apparatus  is  supplied  by  the  Elektrizitats-A-G.  Vorm.  Schuckert 
&  Co.,  Nurnberg.  In  a  private  communication  they  state  that  an  electrolyzer 
battery,  capable,  when  running  at  a  temperature  of  50°  to  60°  C.,  of  producing  hourly 
10  cubic  meters  of  hydrogen,  yields  the  gas  of  99.5  per  cent  purity.  For  this  equip- 
ment they  quote: 

Electrolyzer $2350 

Caustic  soda  (containing  a  little  chlorine  and  sulfur)  1450  kilos  ....         410 

Insulating  material 100 

2  scrubbers,  driers,  and  safety  devices,  pressure  regulators  and 

gauges '     250 

2  gas-purifying  stoves • 500 

Packing  for  over  seas  and  freight 240 

Total $3850 

Other  auxiliaries  are: 

2  gas  holders  (10  and  20  cubic  meters) $2000 

Wooden  staging  and  boxes  to  contain  the  battery  embedded  in 

sand  for  protection  against  loss  of  heat 200 

Compressors 2850 

Water-distilling  apparatus '.-.  200 

Miscellaneous 525 

The  temperature  of  the  electrolyzer  room  should  be  maintained  at  least  at  15°  C. 
In  cold  weather  it  must  be  heated. 

An~electrolytic  hydrogen  and  oxygen  generator  of  the  bell-collector  type  is  de- 
scribed by  Benker  (J.  S.  C.  I.,  1914,  256,  and  French  Patent  461,981,  Aug.  29,  1913). 


278 


THE  HYDROGENATION  OF  OILS 


' 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


279 


gen  and  oxygen  are  given  by  Van  Scoyoc  (U.  S.  Patent  813,844,  Feb.  27,  1906), 
in  which  the  operation  is  rendered  continuous  by  the  use  of  automatic  float-valves. 
The  level  of  the  acidulated  water  in  the  electrolyzer  is  maintained  constant  by 
means  of  a  float- valve  in  the  supply  pipe.  The  two  electrodes  are  placed  in  two 
compartments  which  are  open  at  the  bottom.  Each  compartment  is  divided 
into  a  lower  and  an  upper  chamber,  connection  between  the  two  being  made  by 
automatic  float-valves.  When  the  pressure  of  the  gases  generated  in  the  lower 
chambers  becomes  great  enough  to  lower  the  level  of  the  water,  the  valve  is  opened 
and  the  gases  pass  into  the  other  chamber  and  then  into  gas  bags. 

Aigner*  charges  an  alkaline  electrolyte  into  an  iron  vessel  G,  Fig.  125, 
in  which  an  iron  drum  T  rotates,  the  outer  surface  of  the  latter  being 
amalgamated. 

The  upper  part  of  G  is  divided  into  two  compartments  R  and  RI  by  the  parti- 
tion >S,  which  extends  downwards  nearly  to  the  drum  T.  The  oxygen  and  hydro- 
gen are  led  off  through  separate  outlets  in  the 
cover  D.  The  electrolyte  is  introduced  and  with- 
drawn through  the  opening  L.  At  the  anode  A 
hydroxyl  ions  are  depolarized,  with  formation  of 
water  and  gaseous  oxygen,  the  latter  escaping  into 
the  compartment  R,  while  an  equivalent  quantity 
of  sodium  ions  is  depolarized  and  combines  chem- 
ically with  amalgam  on  the  surface  of  the  drum 
adjacent  to  the  anode.  When  this  portion  of  the 
drum  comes  below  the  cathode  K  hydroxyl  ions 
are  depolarized  with  formation  of  sodium  hydrox- 
ide, the  sodium  being  redissolved  from  amalgam, 
while  sodium  ions  are  depolarized  with  formation 
of  sodium  hydroxide  and  gaseous  hydrogen. 

The  electrodes  of  the  Cowper-Coles 
generatorf  consist  of  metallic  sheets  pro- 
vided with  tongues,  which  project  down- 
wards at  an  angle  of  about  45  degrees  with 

the  faces  of  the  sheets.  These  electrodes  are  placed  in  separate 
collecting  boxes  or  chambers,  the  liberated  gases  being  guided  into 
the  latter  by  the  inclined  tongues  of  metal  which  project  within 
openings  in  the  sides  of  the  chambers.  A  battery  of  generators  may 
be  enclosed  in  a  water  jacket  and  provided  with  means  for  keeping 
the  solution  in  each  cell  at  a  common  level. 

Dansette  (French  Patent  391,793,  Sept.  6,  1907)  has  devised  an  arrangement  for 
feeding  water  vapor  into  the  zone  of  an  electric  arc  produced  in  a  gas-tight  electric 
furnace,  by  passing  water  through  the  lower,  vertical,  carbon  tube,  which  constitutes 
one  of  the  electrodes.  The  furnace  communicates  by  means  of  a  valve  with  a  reser- 
voir, into  which  the  hydrogen  and  oxygen  produced  by  dissociation  pass.  The 
oxygen  may  either  be  absorbed  by  a  suitable  reagent,  or  the  two  gases  separated  by 
diffusion  through  a  porous  earthenware  vessel. 

*  German  Patent  198,626,  Nov.  13,  1906. 
f  British  Patent  14,285,  Dec.  20,  1907. 


FIG.  125. 


280 


THE  HYDROGENATION  OF  OILS 


An  electrolyzer  for  the  production  of  pure  hydrogen  and  oxygen 
which  is  suggestive  of  the  Schmidt  type  has  been  designed  by  Eycken, 
Leroy  and  Moritz.*  The  electrode  plates  are  built  up  with  separating 
diaphragms  of  asbestos,  in  the  form  of  a  filter-press.  Openings  in  the 
top  of  each  plate  form  two  channels  for  the  escape  of  the  gases.  The 
gases  are  kept  at  a  pressure  above  that  of  the  atmosphere,  rendering 
the  danger  of  accidental  mixing  remote.  The  electrodes  and  dia- 
phragms are  kept  clean  by  making  the  first  electrode  hollow,  and  in 
the  form  of  a  large  reservoir,  in  which  the  sediment  accumulates  and 
from  which  it  may  be  removed  from  time  to  time.  This  reservoir  is 
divided  into  two  parts,  into  which  the  gases  pass,  through  the  electro- 
lyte, the  pressure  being  maintained  constant,  and  the  delivery  of  the 
gases  regulated  by  two  floats  and  balanced  valves. 


Go 


Gh 


FIG.  126. 


Siegfried  Earth  of  Dusseldorf  builds  "  oxhydrogenerators "  constructed  in  accord- 
ance with  the  foregoing  system.  The  parts  of  the  generator  are  very  heavy  so  that 
durability  is  insured.  The  electrode  plates  are  insulated  by  extra  heavy,  almost 
indestructible,  diaphragms.  A  very  powerful  circulation  of  the  electrolyte  over  the 
surface  of  the  electrode  is  obtained,  resulting  in  an  efficient  removal  of  the  gas 
particles  which  otherwise  would  cling  to  the  electrodes  for  a  considerably  longer 
period.  Great  pains  have  been  taken  to  guard  against  mixing  of  the  gases  so  as  to 
procure  pure  products.  Caustic  soda  or  potash  in  distilled  water  is  used  as  the 
electrolyte.  When  used  uninterruptedly,  the  cell  becomes  warm  and  its  output  is 
improved,  and  for  intermittent  operation  a  steam-heating  arrangement  is  attached 
to  the  generator  so  that  it  may  be  heated  quickly  and  brought  to  full  capacity  with- 
out loss  of  time.  The  ordinary  type  of  this  generator  is  made  to  deliver  both  hydro- 
gen and  oxygen  under  a  pressure  of  about  50  to  80  cubic  meters  water  column,  but 
special  forms  are  furnished  which  operate  under  a  pressure  of  about  4  kilos  (8  to 
9  pounds).  A  generator  having  an  output  of  6.6  cubic  meters  of  hydrogen  and  3.3 
cubic  meters  of  oxygen  per  hour,  requiring  160  amperes  at  250  volts  is  4.4  meters 

*  French  Patent  397,319,  Dec.  9,  1908. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


281 


long,  0.72  meter  wide,  and  2.05  meters  in  height,  and  weights  6600  kilos;  the  cost 
being  $2175.     (Fig.  126.)* 

Another  apparatus  of  the  filter-press  type  f  is  designed  especially 
to  produce  the  gases  at  relatively  high  pressure  without  the  purity  of 
the  product  being  affected.  Fig.  127  shows  a  form  of  electrode  plate 
and  Fig.  128  a  view  of  one  end  of  the  generator,  showing  a  collecting 
tower  with  regulator  float  and  a  series  of  plate  electrodes.  J§ 

The  electrolytic  cell  of  Tommasini  as  shown  in  Fig.  129  contains 
vertical  anodes  6  and  cathodes  in  the  form  of 
inverted  U-shaped  receptacles  5.  The  outside 
of  these  receptacles  5  is  covered  with  an  insu- 
lating apron  7  which  extends  to  a  point  above 
the  liquid  line,  and  to  a  point  below  the  lower 
edge  of  the  cathode  5  proper,  so  that  an  over- 
hanging apron  8  is  provided.  The  gases  evolved 
at  the  plates  6  and  accumulated  in  the  top  of 
the  inverted  receptacles  5  are  conducted  off  sep- 
arately, the  hydrogen  passing  through  the  pipe 
12  into  the  safety  device  14.  The  height  of 
water  is  less  in  the  safety  device  14  than  in  the 
receptacles  5,  so  that  when  the  ^ 

pressure  of  the  hydrogen  gas  ' 
becomes  so  great  as  to  tend  to 
press  the  fluid  out  of  the  cham- 
bers 5  (which  would  result  in 
the  mixing  of  the  hydrogen  with 
oxygen)  the  pressure  of  the  hy- 
drogen gas  will  first  press  the 
water  out  of  the  receptacle  19 
and  pass  out  of  slots  20,  so  as  to  relieve  the  pressure  in  the  receptacles 
5.  The  aprons  8  at  the  bottom  of  the  compartments  5  also  prevent 
mixing  of  the  two  gases.  || 

*  A  multiple-cell  electrolytic  generator  has  been  patented  by  Levin,  U.  S.  Patent 
1,094,728,  April  28,  1914,  assigned  to  the  International  Oxygen  Co. 

t  Moritz,  U.  S.  Patent  981,102,  Jan.  10,  1911. 

j  In  the  generator  of  L'Oxhydrique  Francaise  (French  Patent  459,967,  Sept.  21, 
1912,  and  addition,  June  25,  1913),  the  diaphragm  of  each  element  is  composed  of 
asbestos  fabric,  which  is  nipped  between  two  wooden  frames.  The  latter  are  bored 
so  as  to  provide  conduits  for  the  evolved  gases  and  the  electrolyte.  The  electrodes 
are  composed  of  light  sheet  iron,  grooved  or  corrugated,  so  as  to  possess  as  much 
active  surface  as  possible.  The  electrodes  may  be  nickelled  on  their  anode  sides. 
The  apparatus  comprises  a  series  of  such  elements. 

§  See  also  U.  S.  Patent  Reissue  13,643,  Nov.  11,  1913. 

II  U.  S.  Patent  1,035,060,  Aug.  6,  1912. 


FIG.  127. 


FIG.  128. 


282 


THE  HYDROGENATION  OF  OILS 


Buffa  (Electrician  (1900),  46)  states  that  one  of  the  chief  difficulties  met  with  in 
the  electrolysis  of  water  on  the  large  scale  is  the  mixing  of  the  oxygen  and  hydro- 
gen given  off  at  the  two  electrodes.  If,  in  order  to  avoid  this  mixing,  a  diaphragm 
be  introduced,  the  resistance  of  the  cell  increases  to  such  an  extent  that  the  efficiency 
of  the  apparatus  is  seriously  reduced.  A  better  method  is  to  use  metallic  septa; 
these  separate  the  two  gases  perfectly,  and  act  as  intermediate  electrodes.  Since 
the  reduction  of  voltage,  both  from  the  anode  to  one  side  of  the  septum  and  from 
the  other  side  of  the  septum  to  the  cathode,  is  insufficient  to  cause  decomposition 


FIG.  129. 

of  the  water,  liberation  of  the  products  of  electrolysis  does  not  occur  at  either  sur- 
face of  the  metallic  septum,  but  is  confined  to  the  electrodes  proper.  In  practice, 
iron  electrodes  in  a  11  per  cent  solution  of  caustic  soda  have  been  found  to  be  most 
convenient  and  economical.  The  electrolyte  is  covered  with  a  film  of  mineral  oil, 
in  order  to  prevent  absorption  of  carbon  dioxide  from  the  air.  It  has  been  observed 
that  the  same  protective  action  is  afforded  by  a  film  of  water  vapor,  which  obtains 
when  the  temperature  of  the  electrode  is  fairly  high ;  when,  however,  the  temperature 
drops  to  10°  C.  or  under,  absorption  of  carbon  dioxide  takes  place  rapidly. 

With  the  object  of  completely  preventing  admixture  of  the  two 
gases  and  at  the  same  time  keeping  the  electrical  resistance  low, 
Vareille  arranges  the  electrodes  as  shown  in  Fig.  130.  Vertical  rows 
of  V-shaped  troughs  are  provided  with  suitable  insulation  and  serve 
to  separate  the  positive  and  negative  electrodes  which  are  placed  on 
opposite  sides.  The  extremities  20  of  these  troughs  are  lower  than 
the  ends  of  the  electrodes  13,  so  that  the  bubbles  of  gas  coming  from 
the  latter  cannot  mix.  The  electrodes  are  both  insulated  from  the 
container.* 

In  a  modification,  the  troughs,  described  above,  for  the  separation  of  the  electrodes 
are  replaced  by  vertical  series  of  elements  each  of  triangular  section,  and  either  solid 
or  hollow.  Each  electrode  consists  of  a  sheet,  with  U-shaped  pieces  bound  on  each 
side  with  rivets.  The  gases  are  collected  in  bells,  either  stamped  out  of  sheet  metal 
or  consisting  of  sheets  cut  out  and  folded,  and  united  at  the  angles  by  autogenous 
soldering,  f 

*  French  Patent  355,652,  June  27,  1905,  and  U.  S.  Patent  823,650,  June  19,  1906. 

t  First  addition,  Oct.  28,  1908,  to  French  Patent  355,652. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


283 


Water  is  made  more  conductive,  according  to  McCarty  (U.  S.  Patent  736,868, 
Aug.  18,  1903),  by  the  addition  of  tartrate  of  potassium,  tartrate  of  sodium,  or  any 
of  the  citrates  or  other  equivalents,  and  sulfuric  acid.  The  apparatus  (U.  S.  Patent 
721,068,  Feb.  17,  1903)  consists  of  two  tanks,  connected  by  a  pipe  at  about  half 
their  height.  Each  tank  consists  of  an  electrode,  so  located  that  the  upper  ends 
are  about  in  a  line  with  the  axis  of  the  connecting  pipe,  through  which  the  current 
passes  from  one  tank  to  the  other.  Each  of  the  two  tanks  has  an  outlet  at  the  top 
through  which  the  gases  generated  may  be  led  to  suitable  holders. 


FIG.  130. 


FIG.  131. 


Another  apparatus  (McCarty,  U.  S.  Patent  816,355,  March  27,  1906)  consists 
of  two  receptacles,  each  containing  one  electrode  and  connected  by  a  conduit  near 
the  bottom.  Each  electrode  is  a  plate  of  platinum  coiled  upon  itself  a  number  of 
times  and  has  a  projecting  terminal  portion  directly  opposite  the  end  of  the  conduit. 
In  still  another  type  (McCarty,  814,155,  March  6;  see  also  813,105,  Feb.  20,  1906) 
the  electrolytic  cell  is  divided  into  two  compartments  by  means  of  a  solid  diaphragm, 
which  is  perforated,  short  glass  tubes  being  inserted  in  each  perforation. 

The  Burdett  system  *  of  electrolytic  apparatus  consists  of  a  varying 
number  of  generators  or  units,  connected  electrically  in  series.  The 
unit,  Fig.  131,  comprises  a  container  enclosing  the  electrodes  and  electro- 
lyte, but  the  walls  of  the  container  do  not  function  as  electrodes.  It 
is  usually  mounted  on  concrete  foundations  and  is  insulated  both  from 
the  ground  and  from  the  generator  proper.  The  electrodes  are  ar- 
ranged on  the  multiple  system,  there  being  a  number  of  both  positive 
and  negative  electrodes  in  each  unit.  The  electrodes  are  separated 
from  each  other  by  a  partition  of  specially-prepared  asbestos  cloth 
which  under  the  conditions  of  operation  is  permeable  to  the  solution 
but  not  to  gas. 

*  U.  S.  Patent  to  Burdett,  1,086,804,  Feb.  10,  1914. 


284  THE  HYDROGENATION  OF  OILS 

A  bell  or  box  casting,  open  at  the  bottom,  is  used  for  housing  the 
electrodes  and  the  asbestos  diaphragm  is  stretched  across  the  box 
casting  from  one  side  to  the  other,  forming  a  number  of  compartments. 
In  each  of  the  compartments  an  electrode  is  placed  running  parallel 
to  the  asbestos  curtain  or  diaphragm.  The  electrical  connections  are 
so  arranged  that  commencing  with  and  including  the  first  electrode, 
every  other  electrode  is  a  cathode,  the  alternate  electrodes  being 
anodes.  At  the  top  of  the  container  the  electrode  terminals  are  joined 
by  means  of  copper  bus  bars,  thus  bringing  all  the  anodes  to  a  common 
anode  terminal  and  all  of  the  cathodes  to  a  similar  connection. 

The  gas  generated  at  the  electrodes  rises  and  is  collected  in  the 
separate  gas-tight  compartments.  These  compartments  are  joined 
by  two  cored  gas  passages  in  the  bell  casting  and  the  gases  pass  through 
these  passages  into  and  through  glass  indicators  and  purgers  to  the 
gas  mains.  Inserted  in  each  of  the  service  mains  is  a  gas  meter,  a 
flash-back,  and  a  water  purger  which  removes  the  water  held  in  sus- 
pension in  the  gas  and  at  the  same  time  acts  as  a  pressure  regulator 
for  the  generators.  Purifiers  are  usually  inserted  in  each  line  to 
cleanse  the  gas.  The  hydrogen  and  oxygen  are  led  to  their  respective 
gasometers  and  from  there  are  compressed  into  storage  tanks  for  use. 
By  means  of  controls  the  compression  may  be  taken  care  of  auto- 
matically.* 

The  automatic  control  feature  of  the  Burdett  apparatus  is  useful. 
By  means  of  electrical  regulating  devices  the  entire  electrolytic  equip- 
ment is  under  automatic  control.  It  also  serves  as  a  safety  device, 
preventing  over-generation  of  gas  or  undue  pressure  on  any  parts 
of  the  apparatus.  The  compressor,  when  the  collecting  gasometer 
reaches  a  predetermined  height,  will  automatically  start,  and  will 
stop  when  the  gasometer  falls  to  a  predetermined  level.  Electric 
control  is  provided  which  will  stop  the  motor  of  the  compressor 
when  the  storage  tank  pressure  reaches  a  certain  point,  starting  the 
motor  when  the  pressure  falls  again,  and  another  control  is  provided 
which  will  stop  the  generation  of  gas  when  both  gasometer  and  storage 
tank  are  charged  to  their  full  capacity. 

Fig.  132  shows  a  battery  of  Burdett  generators  and  Fig.  133  illustrates 
a  complete  equipment  embracing  motor-generator,  gasometers,  storage 
tanks  and  automatic  control  devices. 

Each  generator  operating  under  a  current  of  400  amperes  will  produce  in  excess 
of  6  cubic  feet  of  hydrogen  and  one-half  this  amount  of  oxygen  per  hour,  or  in  round 
numbers,  150  cubic  feet  of  hydrogen  and  75  cubic  feet  of  oxygen  per  24-hour  day 

*  The  author  is  indebted  to  Mr.  Paul  Pleiss  for  a  description  of  the  Burdett 
generator,  also  for  some  data  on  the  Garuti  and  Schuckert  cells. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


285 


with  the  gas  measured  at  20°  C.  and  760  mm.     It  is  desirable  to  operate  the  plant 
as  continuously  as  possible  and  a  run  of  23  or  24  hours  per  day  is  recommended. 

Each  cell  operating  under  normal  conditions  will  require,  with  a  solution  temper- 
ature of  80°  F.  about  2  volts  for  the  passage  of  400  amperes.  Thus  each  cell  requires 
about  800  watts  (0.8  kilowatt-hour)  per  hour  to  produce  about  6  cubic  feet  of 


FIG.  132. 

hydrogen  per  hour.  The  efficiency  of  the  generator  is  therefore  high.  If  the  cell 
generator  be  artificially  heated  the  consumption  of  electricity  may  be  decreased 
by  about  10  per  cent  with  a  corresponding  increase  in  the  efficiency  of  the  unit. 
The  hydrogen  will  average  in  purity  99  per  cent  or  higher. 


FIG.  133. 


Electrolytic  apparatus  designed  by  Hazard-Flamand  *  is  shown  in 
Fig.  134.  Between  the  inner  and  outer  electrodes  a  porous  diaphragm 
is  inserted  and  a  fluid  seal  is  disposed  about  both  sides  of  the  top  of  the 


*  U.  S.  Patent  1,003,456,  Sept.  19,  1911,  assigned  to  the  International  Oxygen 


Co. 


286 


THE  HYDROGENATION  OF  OILS 


diaphragm  and  is  composed  of  an  outer  seal  and  an  inner  seal,  con- 
sisting of  two  concentric  troughs  one  within  the  other.  The  elec- 
trolyte is  fed  into  the  inner  trough,  passes  to  the  outer  trough  and 
is  delivered  from  the  latter  on  both  sides  of  the  diaphragm.* 


FIG.  134. 

The  I.  O.  C.  System  (International  Oxygen  Co.)  is  a  well-standard- 
ized method  of  generating  hydrogen  and  oxygen.  The  electrolytic 
cell  used  is  very  simple,  an  outside  view  being  given  in  Fig.  135  and  a 
diagram  in  Fig.  136.  The  iron  tank  or  container  serves  as  the  cathode, 
being  connected  to  the  negative  pole  of  the  electric  supply  circuit. 
From  the  cover  of  this  tank  is  suspended  a  perforated  tank  which 
serves  as  the  anode,  being  connected  to  the  positive  pole  of  the  supply 
circuit.  It  is  made  of  a  specially  selected  low-carbon  steel,  to  pre- 
vent the  formation  of  spongy  rust.  By  means  of  an  asbestos  sack, 
suspended  from  the  cover  between  anode  and  cathode,  two  separate 
compartments  are  formed.  At  the  top  these  compartments  are 
sealed  by  a  hydraulic  joint.  Through  an  opening  in  the  cover  a  solu- 
tion of  caustic  alkali  in  distilled  water  is  poured  into  the  hydraulic 

*  See  also  U.  S.  Patent  646,281,  March  27,  1900,  to  Hazard-Flamand. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         287 


FIG.  135. 


SECTIONAL    VIEW 

I.O.C.  GENERATOR  TYPE  20tt 


FIG.  136. 


288 


THE  HYDROGENATION  OF  OILS 


joint  and  distributed  in  the  two  compartments.     The  whole  cell  is 
placed  on  insulating  supports  of  porcelain. 

The  oxygen  and  hydrogen  gases  evolved  do  not  pass  directly  from 
their  compartments  to  the  off-take  pipes,  but  first  bubble  through 
water  contained  in  the  two  " lanterns"  on  top  of  the  cell.  They  enable 
the  operator  to  see  at  a  glance  how  the  cell  is  working.  The  purity 
of  the  gases  produced  is  very  high.  A  sample  of  hydrogen  produced 


FIG.  137.     Battery  of  I.  O.  C.  generators. 

by  this  electrolyzer,  analyzed  by  the  Conservatoire  National  des  Art 
et  Metier  in  Paris,  showed  99.70  per  cent  hydrogen,  the  fraction  of 
the  impurities  being  so  small  that  they  were  not  examined. 

All  that  is  required  for  the  operation  of  the  cell  is  the  daily  addition 
of  somewhat  over  a  gallon  of  distilled  water  to  make  up  for  the  quan- 
tity decomposed  into  hydrogen  and  oxygen.  The  daily  output  is 
approximately  72  cubic  feet  of  oxygen  and  144  cubic  feet  of  hydrogen. 
As  to  the  electrical  energy  requirements  a  joint  test  *  made  in  Novem- 
ber, 1910,  by  the  Laboratoire  Centrale  de  PElectricite  and  the  Con- 
servatoire National  des  Arts  et  Metier  with  two  unit  cells  of  this  type 
of  electrolytic  cell  showed  that  the  production  of  1  cubic  foot  of  oxy- 

*  Met.  and  Chem.  Eng.  (1911),  471. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         289 


gen  and  2  cubic  feet  of  hydrogen  requires  0.2797  kilowatt-hour.  Re- 
versely 1  kilowatt-hour  produces  3.54  cubic  feet  of  oxygen  and  7  cubic 
feet  of  hydrogen.  Each  unit  cell  requires  a  little  above  2  volts  and 
from  300  to  400  amperes.  A  current  of  350  amperes  produces  about 
65  cubic  feet  of  oxygen  and  130  cubic  feet  of  hydrogen  per  day. 


FIG.  138. 

The  following  table  gives  the  results  of  a  test  recently  made  by  the  Electrical 
Testing  Laboratories  of  New  York  for  the  International  Oxygen  Co. 


Cell  No. 

Average 
am- 
peres 

\verage 
volts 

Average 
watts 

Maximum 
temp. 

Purity  of 
oxygen 

Cubic  feet 
per  hour 

Cubic  feet  per 
kilowatt-hour 

Oxy- 
gen 

Hydro- 
gen 

Oxy- 
gen 

Hydro- 
gen 

8 

405.1 
405.0 
368.8 
392.0 

2.388 
2.562 
2.826 
2.660 

967 
1038 
1042 
1043 

31.  8°  C. 
30.0°C. 
32.0°C. 
26.  5°  C. 

97.73% 

98.67% 
98.46% 
98.50% 

3.247 

3.239 
2.886 
3.082 

6.184 

5^788 
6.254 

3.358 

3.120 
2.770 
2.955 

6.395 

5^555 
5.900 

5.950 

14 

66 

70  

Average 

392.7 

2.609 

1022 

30.1°C. 

98.34% 

3.114 

6.075 

3.051 

290 


THE  HYDROGENATION  OF  OILS 


The  four  cells  tested  were  selected  as  being  representative  of  the  entire  battery 
after  taking  a  set  of  preliminary  electrical  measurements  on  each  of  the  cells. 

All  of  the  data  given  herewith  are  from  readings  as  actually  observed  and  cor- 
rected for  instrument  errors.  Gas  volumes  are  corrected  for  moisture  and  calculated 
to  20°  C.  and  760  mm. 


FIG.  139. 


The  main  item  of  operating  expense  is  the  cost  for  the  electric  current.  In  New 
York  City  the  wholesale  rates  are  higher  than  in  many  other  large  cities  and  vary  from 
5  to  3  cents  per  kilowatt-hour,  according  to  the  size  of  the  plant;  since  1  kilowatt- 
hour  produces  about  3  cubic  feet  of  oxygen  and  6  cubic  feet  of  hydrogen,  the  electric 
power  cost  for  producing  1000  cubic  feet  of  oxygen  and  at  the  same  time  2000  cubic 
feet  of  hydrogen  would  be  between  $16.70  and  $10.00.  However,  in  large  manu- 
facturing plants  which  have  their  own  power  houses  the  cost  of  energy  is  much 
less;  thus  it  is  known  that  at  the  South  Chicago  works  of  the  U.  S.  Steel  Corporation 
the  electrical  energy  supplied  to  the  electric  furnaces  is  charged  at  the  rate  of  half 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER         291 

a  cent  per  kilowatt-hour.      At  this  rate  the  electric  power  cost  for  producing  1000 
cubic  feet  of  oxygen  and  2000  cubic  feet  of  hydrogen  would  be  $1.67. 

Besides  the  electric  power  cost  there  is  the  cost  for  distilled  water  and  for  attend- 
ance. The  latter  is  a  small  item,  and  the  cost  for  the  distilled  water  which  must  be 
added  to  the  cells  to  make  up  for  the  water  electrolyzed  may  be  calculated  from 
the  fact  that  a  little  over  6  gallons  of  distilled  water  are  required  to  produce  1000 
cubic  feet  of  hydrogen. 

One  of  the  objections  advanced  against  the  electrolytic  system  is 
the  relatively  large  floor  space  which  it  occupies,  and  to  obtain  an 
apparatus  of  a  durable  yet  compact  character  the  author  has  designed 
a  generator  having  T-shaped  ribs  on  both  anode  and  cathode,  afford- 
ing a  large  generating  surface  without  excessive  bulk.  Fig.  138  shows 
a  form  of  anode  and  Fig.  139  the  assembled  generator.* 

*  U.  S.  Patent  1,087,937,  Feb.  24,  1914. 


CHAPTER  XX 
SAFETY  DEVICES 

The  handling  of  electrolytically-derived  gases  brings  with  it  the 
possibility  of  explosions  due  to  accidental  mixing  of  the  two  gases, 
and  to  guard  against  serious  results,  at  frequent  intervals  in  the  con- 
nections of  the  apparatus  and  service  pipes,  safety  devices  should  be 
inserted. 

The  common  form  of  safety  device  is  the  wire-gauze  arrangement 
of  Sir  Humphrey  Davy.  It  usually  consists  of  a  roll  of  wire  gauze  or 
a  number  of  disks  of  gauze  inserted  in  the  pipe  connections.  Such 
arrangements  sometimes  will  check  the  progress  of  an  explosion  tem- 
porarily or  completely,  but  as  a  rule  when  an  explosion  wave  passes 
along  the  pipe  in  which  the  wire  gauze  is  placed,  although  checked 
temporarily  by  the  wire-gauze  obstruction,  it  soon  heats  the  latter  to 
the  ignition  point.  Thus  the  gas  on  the  other  side  of  the  gauze  is 
ignited  and  the  explosion  wave  continues  on  its  course. 


FIG.  140. 

When  wire  gauze  is  used  preferably  it  should  take  the  form  shown 
in  Fig.  140.  A  spool  a  carries  perforations  along  its  stem  and  over 
this  wire  gauze  is  wound  to  make  a  thick  layer.  The  spool  is  placed 
in  the  holder  6  and  fitted  tightly  in  place  against  a  rubber  gasket  so 
that  gases  entering  one  end  of  b  will  pass  along  the  hollow  stem,  flow 
through  its  perforations  and  those  of  the  gauze  and  make  their  exit 
at  the  opposite  end  of  b. 

Glass  wool  obstructs  explosion  waves  in  a  fairly  satisfactory  manner 
if  it  is  inserted  into  the  pipe  connections  in  such  a  way  as  to  fill 
the  cross-sectional  area  without  being  packed  so  tightly  as  to  greatly 

292 


SAFETY  DEVICES 


293 


reduce  the  flow  of  gas.  Layers  of  glass  wool,  or  finely-divided  re- 
fractory material,  such  as  fire-brick  granules  of  about  20  mesh,  alter- 
nated with  bundles  of  wire  gauze,  may  be  packed  into  pipes  of 
relatively  large  diameter  to  form  an  excellent  safety  device,  which  is 
rendered  even  more  reliable  if  placed  in  a  tank  of  water  so  as  to  be 
kept  cool  in  event  an  explosion  wave  causes  ignition  of  the  gas  at  the 
surface  of  the  outer  layer. 

It  is  stated  by  Schoop  that  under  the  conditions  occurring  in  prac- 
tice explosion  mixtures  are  formed  when  either  gas  contains  by  vol- 
ume 6  to  8  per  cent  of  the  other  gas.  Such  an  impurity  may  quite 
readily  occur  through  injury  to  the  diaphragm  of  cells  of  the  asbestos- 
diaphragm  type,  and  in  constructions  similar  to  the  Garuti  cell  care 
should  be  taken  to  prevent  an  excess  voltage  which  will  render  the 
diaphragms  bipolar. 

Boynton's  device  for  preventing  the  transmission  of  explosions  is 
shown  in  Fig.  141.  A  is  the  gas  inlet,  B  the  outlet,  E  one  or  more 
perforated  plates  and//  a  space  filled  with  fragments  of  metal.* 


FIG.  141. 

For  the  prevention  of  hydrogen  explosions  steel  wool  is  recommended 
by  Ohmann.f  He  regards  steel  wool  as  very  suitable  to  take  up 
and  carry  off  the  heat  developed  and,  by  lowering  the  temperature 
in  this  way,  preventing  the  spreading  of  an  explosion.  To  insure 
against  the  danger  of  an  explosion,  a  roll  of  the  wool,  somewhat 
tightly  pressed  together,  is  placed  in  the  gas  conduit.  Trials  with  a 
mixture  of  f  hydrogen  and  f  air,  also  with  the  strongest  explosive 
gas  mixture  2  H  +  O,  showed  that  the  explosive  flame  or  wave  was 
checked  and  extinguished  in  contact  with  the  wool. 

*  U.  S.  Patent  58,055,  Sept.  18,  1866.  See  also  U.  S.  Patents  713,421,  730,807, 
743,064,  819,202  and  948,323. 

t  Z.  physik.  chem.  Unterricht,  11,  272;  Chem.  Zentr.  (1912),  1,  1426. 


294 


THE  HYDROGENATION  OF  OILS 


The  various  possible  causes  of  certain  fatal  accidents  resulting  from 
the  explosion  of  oxygen  or  hydrogen  cylinders  has  been  discussed  by 
Bramkamp.* 

In  most  cases  it  is  certain  that  an  explosive  mixture  of  hydrogen 
and  oxygen  has  been  introduced  into  the  cylinder.  The  two  most 

important  causes  of  this  are:  (1) 
the  use  of  the  same  compressor  al- 
ternately for  both  gases;  and  (2) 
unsatisfactory  control  and  atten- 
tion-when  the  gases  are  obtained  at 
the  same  time  in  the  electrolysis 
of  water.  Other  causes  which  may 
contribute  but  which  are  unlikely 
in  themselves  to  account  for  an  ex- 
plosive mixture  in  a  full  cylinder 
are:  (1)  the  use  of  an  oxygen  cylin- 
der as  a  hydrogen  cylinder  or  vice 
versa,  without  previously  removing 
all  the  original  gas;  and  (2)  the 
absorption  of  hydrogen  by  finely- 
divided  iron  inside  the  cylinder. 
The  various  methods  by  which  the 
explosive  mixture  when  present 
may  be  exploded  include:  (1)  igni- 
tion of  oil  or  other  combustible 

material  in  the  valve  or  pressure  gauge  by  the  compressed  oxygen; 
(2)  local  rise  in  temperature  of  the  gas  due  to  sudden  closing  of  the 
valve;  (3)  catalytic  action  of  finely-divided  iron  in  causing  combina- 
tion in  the  mixture  and  raising  its  temperature;  and  (4)  pyrophoric 
oxidation  of  finely-divided  iron.  Bramkamp  is  of  the  opinion  that 
with  suitable  precautions  an  explosive  mixture  need  never  be  put 
into  a  cylinder,  and  that  all  cylinders  should  be  tested  by  analysis 
of  their  contents  immediately  after  filling. 

Tubes  of  compressed  hydrogen,  accidentally  contaminated  with 
air,  have  been  known  to  -explode  on  connecting  them  with  a  manom- 
eter for  the  purpose  of  measuring  the  pressure  of  the  gas.  Lelarge  f 
has  found  that  if  ordinary  manometers  are  employed  in  the  usual  way, 
such  explosions  may  occur  whenever  the  hydrogen  contains  enough 
air  to  render  it  explosive,  and  the  pressure  is  sufficiently  high.  The 
reason  probably  lies  in  the  rise  of  temperature  produced  by  the  sudden 

*  Zeit.  ang.  Chem.  (1912),  536. 
t  Compt.  rend.  (1912),  914. 


FIG.  142.     High-pressure  cylinders 
for  hydrogen. 


SAFETY  DEVICES 


295 


FIG.  143.    Compressor  for  compressing  hydrogen  or  oxygen  into  cylinders. 


296  THE  HYDROGENATION   OF  OILS 

and  more  or  less  adiabatic  compression  of  the  air  in  the  manometer. 
Such  accidents  may  be  avoided  by  interposing,  between  the  tube  of 
compressed  gas  and  the  manometer,  a  safety-tube  containing  discs  of 
metallic  gauze  of  such  mass  that  they  are  not  appreciably  heated  by 
combustion  of  the  gas  mixture  in  the  manometer.  By  this  means  the 
ignition  of  the  main  body  of  gas  is  prevented.  Similar  safety-tubes 
should  be  employed  whenever  a  highly-compressed  explosive  gas  mix- 
ture is  allowed  to  expand  suddenly  into  a  confined  space.  Before 
measuring  the  pressure  of  compressed  hydrogen,  liable  to  contain  air 
or  oxygen,  it  is  advisable  to  determine  its  density,  as  a  further  safe- 
guard. 

SUMMARY 

The  majority  of  the  numerous  proposals  for  making  hydrogen  in 
various  ways  have  been  outlined  in  the  foregoing  for  the  reason  that 
many  investigators  at  the  present  time  are  studying  the  subject  of 
hydrogen  generation,  and  everywhere  present  and  prospective  users  of 
hydrogen  are  seeking  information  which  may  enable  a  better  under- 
standing of  the  subject. 


FIG.  144.     Pressure  tank  for  storage  of  hydrogen. 

For  oil  hydrogenation  at  least  four  methods  of  generating  hydrogen 
are  likely  to  find  a  place.  These  are  the  (1)  steam-iron,  (2)  water-gas 
liquefaction,  (3)  water-gas  and  lime  and  (4)  electrolytic  systems. 
With  the  exception  of  the  latter  these  all  require  a  water-gas  plant 
with  a  n|ot  wholly  simple  system  of  purifiers,  etc.  As  to  the  steam- 
iron  method  it  may  be  noted  that  the  opponents  of  this  system  claim 
it  has  been  shown  in  practice  that  the  iron  sponge  will  not  regenerate 
after  a  few  operations  and  the  iron  retorts  used  are  demolished  all  too 
soon  by  the  high  heat  employed  and  have  to  be  continually  replaced. 
The  advocates  of  the  system  claim  great  improvement  in  the  matter 
of  longevity  of  the  iron  sponge  and  also  figure  on  a  cost  of  production 


SAFETY  DEVICES  297 

around  90  cents  to  $1.00  per  1000  cubic  feet  of  hydrogen.  It  is  doubt- 
ful if  this  figure  generally  could  be  reached  and  so  far  as  the  author 
can  ascertain  the  cost  in  this  country  with  plants  of  moderate  size 
is  approximately  $1.50  per  M.  The  liquefaction  system,  although 
scarcely  feasible  to  install  in  a  small  way,  should  prove  attractive  for 
large  scale  operation  as  the  cost  of  production  is  not  over  $1.00  to  $1.20 
per  M  for  gas  of  very  fair  purity.  The  objection  has  been  raised  that 
the  by-product  of  carbon  monoxide  under  high  pressure  is  dangerous 
to  handle.  The  water-gas  and  lime  system  from  the  point  of  view  of 
low  cost  of  operation  has  much  in  its  favor,  but  has  as  yet  received 
no  extensive  technical  application.  The  electrolytic  process  may  be 
called  the  foolproof  system,  as  with  proper  safeguards  against  mixing 
of  the  gases  and  suitable  safety  devices,  the  generating  plant  may  be 
operated  with  unskilled  labor.  The  objections  raised  against  it  are 
the  floor  space  required  and  the  high  cost  of  the  gas.  If,  however, 
the  oxygen  is  saved  and  compressed  it  can  usually  be  sold  at  a  profit 
which,  credited  against  the  hydrogen  account,  greatly  reduces  the  cost 
of  the  latter.  For  small  plants  electrolysis  has  much  in  its  favor.* 

PURIFICATION  OF  HYDROGEN 

In  the  previous  discussion  of  methods  of  producing  hydrogen  various 
procedures  of  purification  have  been  mentioned.  To  summarize, 

*  The  cost  of  hydrogen  per  cubic  meter  (1  cubic  meter  =  35.3  cubic  feet)  pro- 
duced in  various  ways  is  given  by  Sander  (Zeitsch.  f.  angew.  Chem.  (1912),  2407) 
as  follows: 

Stationary  Plants 

Cents 
Acetylene  (Carbonium)  ......................................     3£ 

Steam  (Internat.  Wasserstoff)  ................................  2£-5 

Water  gas  (Griesheim-Elektron)  ..............................  H-2J 

Water  gas  (Linde-Frank-Caro)  ...............................  2J-3J 

Oil  gas  (Rincker  and  Wolter)  ................................. 


Portable  Plants 

Cents 
Iron  and  sulfuric  acid  ......................................     12|-20 

Aluminium  and  caustic  soda  ...............................  about  62J 

Silicon  and  caustic  soda  ...................................      17£-20 

Ferro-silicon  and  caustic  soda  ...............................      17^-20 

Calcium  hydride  ..........................................  about  $1.00 

Hydrogenite  (Jaubert)  .....................................  about  37  J 

Maricheau-Beaupre  system  ................................  about  37$ 

Activated  aluminium  (Griesheim-Elektron)  ...................  about  45 

Sachs  (Zeitsch.  f.  angew.  Chem.  (1913),  No.  94,  784)  believes  the  cheapening  of 
the  cost  of  manufacture  of  hydrogen  due  to  the  demand  for  this  gas  in  air  ship  prac- 
tice is  in  part  responsible  for  the  rapid  development  of  oil  hardening  processes. 


298  THE  HYDROGENATION  OF  OILS 

oxygen  may  be  eliminated  by  passing  the  gas  through  heated  tubes 
containing  copper  turnings;  carbon  dioxide  by  exposure  to  hydrated 
lime,  carbon  monoxide  by  contact  with  soda  lime  at  300°  C.  or  over,  in 
the  presence  of  moisture,  or  with  acid  cuprous  chloride;  and  nitrogen 
may  be  removed  by  exposure  to  heated  calcium  carbide.  Moisture 
may  be  reduced  to  a  negligible  amount  by  means  of  quicklime,  cal- 
cium chloride  or  other  desiccating  agent. 

Catalyzers  of  'different  types  vary  considerably  in  their  resistance 
to  impurities  or  catalyzer  poisons  in  the  hydrogen,  but  the  period  of 
activity  of  the  more  reliable  catalyzers  is  at  best  all  too  short,  and  it 
may  be  laid  down  as  a  general  rule  that  hydrogen  free  from  moisture, 
oxygen,  sulfur,  phosphorus,  chlorine,  arsenic  and  cyanogen  compounds 
should  be  employed.  Of  course  there  are  exceptions  to  this,  as,  for 
example,  with  nickel  oxide  catalyzers  oxygen  is  thought  not  to  be 
detrimental  and  in  fact  by  some  is  regarded  as  advantageous. 

The  Badische  Anilin  und  Soda-Fab rik  *  remove  traces  of  carbon 
monoxide  from  hydrogen  by  passing  the  gases  through  caustic  alkali 
solutions  at  high  temperatures  and  pressures,  e.g.,  hydrogen  contain- 
ing 1  per  cent  of  carbon  monoxide  is  treated  with  (a)  an  80  per  cent 
solution  of  caustic  soda  at  50  atmospheres  pressure  at  260°  C.,  or  (6) 
a  25  per  cent  solution  of  caustic  soda  at  200  atmospheres  pressure  at 
240°  C.f 

Hydrogen  prepared  from  commercial  zinc  and  acid,  is  bubbled 
through  petroleum  spirit  cooled  by  liquid  air.  A  temperature  of 
110°  C.,  according  to  Renard,{  suffices  to  insure  the  removal  in  this 
way  of  all  the  arseniuretted  hydrogen  even  from  a  rapid  stream  of  the 
gas. 

Wentzki  removes  arseniuretted  hydrogen  from  impure  hydrogen 
by  passing  the  gas  upwards  through  a  cylinder  packed  with  a  mixture 
of  two  parts  of  dry  chloride  of  lime  and  one  part  of  moist  sand  or  other 
inert  material.  If  the  column  of  purification  material  be  sufficiently 
high,  the  whole  of  the  arsenic  is  retained.  A  small  quantity  of  chlorine 
is  set  free,  but  can  be  removed  by  passing  the  hydrogen  through  a 
second  cylinder  packed  with  nearly  dry  slaked  lime.§ 

Rabenalt  ||  purifies  hydrogen  by  passing  it  into  a  solution  of  iodine 
through  which  an  electric  current  is  simultaneously  conducted. 

*  French  Patent  439,262,  Jan.  22,  1912. 

t  By  heating  a  solution  of  caustic  alkali  under  a  pressure  greater  than  five  at- 
mospheres, hydrogen  is  freed  from  sulfur  and  sulfur  compounds.  (Badische,  British 
Patent  14,509,  June  23,  1913.) 

%  Compt.  rend.  (1903),  136  (22),  1317. 

§  Chem.  Ind.  (1906),  405. 

II  U.  S.  Patent  1,034,646,  Aug.  6,  1912. 


SAFETY  DEVICES 


299 


FIG.  145. 


For  purifying  electrolytic  gases  Knowles  *  uses  the  apparatus  as 
shown  in  Fig.  145.  The  gas  to  he  purified  is  first  passed  through  an 
ordinary  washer  then  through  an  explosion  trap  and  finally  enters  the 
purifier  proper.  In  its  entry  into  the  purifier  the  in-going  gas  is  pre- 
heated by  passage  around  the  conduit  through  which  the  out-going 
gas  and  vapor  is  passing.  In  the 
purifying  chamber  the  gas  passes 
through  contact  material  and 
water  vapor  is  formed  and  is  con- 
densed and  removed.  In  the 
illustration  the  web  k  supports 
grids  I  of  porcelain  on  which 
the  contact  material  is  spread. 
Knowles  states  that  when  the 
apparatus  is  working  properly  no 
external  heat  is  required  on  ac- 
count of  the  rise  in  temperature 
caused  by  the  condensation. 

The  removal  of  sulfur  from  gas  by  the  Carpenter  process  f  involves 
passing  the  gas  over  reduced  nickel  heated  to  800°  to  900°  F.  when 
carbon  bisulfide  reacts  with  hydrogen  to  form  hydrogen  sulfide  and  the 
latter  body  is  absorbed  in  the  usual  manner. 

The  treatment  of  water  gas  to  separate  pure  hydrogen,  as  described 
by  Frank, t  is  of  interest  in  this  connection.  Water  gas,  previously 
dried  as  much  as  possible,  is  conducted  over  calcium  carbide,  at  a 
temperature  from  300°  C.  up  to  the  melting  point  of  the  carbide. 
When  water  gas  is  conducted  over  carbide  thus  heated  an  absorption 
of  all  the  substances  associated  with  the  hydrogen  takes  place.  Car- 
bon monoxide  or  dioxide  forms  with  the  carbide,  lime  or  carbonate 
of  lime  and  carbon.  The  nitrogen  is  likewise  absorbed.  The  hydro- 
carbons are  decomposed  when  passed  over  the  heated  lime-carbon 
material  with  the  separation  of  carbon.  The  action  of  the  carbide 
on  various  gases  is  indicated  by  Frank  in  the  following  reactions: 

CO  +  CaC2  =  CaO  +  3  C 
CO2  +  2  CaC2  =  2  CaO  +  5  C 
3  C02  +  2  CaC2  =  2  CaCO3  +  5  C 
O  +  CaC2  =  CaO  +  2  C 
2  N  +  CaC2  =  CaN2C  +  C 

*  U.  S.  Patent  1,073,246,  Sept.  16,  1913. 
t  Jour.  Ind.  &  Chem.  Eng.  (1914),  262. 
j  U.  S.  Patent  964,415,  July  12,  1910. 


300  THE  HYDROGENATION  OF  OILS 

SiH4  +  3  CO  +  CaC2  +  heat  =  CaSi03  +  5  C  +  4  H 

CS2  +  CaC2  =  2  CaS  +  3  C 

H2S  +  CaC2  =  CaS  +  C2  +  H2 

zPH3  +  CaC2  =  CaP*  +  C2  +  3  xH 

CS2  +  2  C02  +  heat  =  2  S02  +  3  C 

2  S02  +  3  C  +  2  CaC2  =  CaS04  +  CaS  +  7  C. 

Almost  chemically  pure  hydrogen  is  ultimately  obtained  as  the  final 
product.  Carbon  monoxide  or  dioxide  may  be  previously  entirely 
or  partially  removed  from  the  water  gas  by  mechanical  separation 
of  the  constituent  gases  to  relieve  the  carbide  from  the  duty  of  sepa- 
rating the  major  part  of  the  gases.  If  the  water  gas  is  produced  at  a 
high  furnace  temperature  and  contains  in  addition  to  hydrogen  almost 
exclusively  carbon  monoxide  and  only  a  little  carbon  dioxide,  the 
mechanical  separation  is  preferably  effected  by  conducting  the  water 
gas,  which  has  been  suitably  cooled,  into  a  Linde's  air-liquefaction 
machine  or  other  similarly  constructed  apparatus  to  liquefy  the  car- 
bon monoxide;  the  dioxide  and  small  quantities  of  silicon-hydrogen, 
etc.,  being  obtained  solid,  whereas  the  hydrogen  remains  gaseous  and 
can  he  separated  and  conducted  away.  If  the  water  gas  is  produced 
at  a  low  temperature,  and  if  little  carbon  monoxide  and  principally 
carbon  dioxide  are  obtained  in  addition  to  hydrogen,  the  previous 
mechanical  separation  may  be  effected  by  the  water  gas  being  cooled 
down  to  a  temperature  below  that  of  the  congealing  or  liquefying 
point  of  the  secondary  constituents  of  the  water  gas  (carbon  dioxide, 
carbon  monoxide,  etc.),  these  secondary  constituents  being  separated 
in  this  manner  in  a  solid  or  liquid  form  from  the  hydrogen  which  is 
obtained.  After  the  previous  mechanical  separation  of  the  secondary 
gases,  the  hydrogen  which  contains  some  remnant  of  other  gases,  as 
CO,  CO2,  SiH4,  H2S,  PH3,  N,  CS2,  and  hydrocarbons,  is  then  subjected 
to  a  final  purification  by  conducting  it  over  carbide.  Before  being 
passed  over  the  carbide,  the  water  gas  may  be  freed  from  carbon 
dioxide  and  monoxide  by  treatment  with  lime  and  cuprous  chloride 
solution  respectively.* 

*  French  Patent  371,814,  Nov.  26,  1906. 


APPENDIX 

HYDROGENATED  OIL  PATENT  LITIGATION 

The  general  interest  awakened  by  litigation  in  England  over  the 
Normann  patent,  together  with  the  fact  that  the  testimony  given  has 
brought  out  much  of  interest  to  investigators  in  the  hydrogenation 
field,  has  led  to  the  inclusion  of  a  report  of  the  Court  proceedings 
which  is  here  given  substantially  as  published  in  the  British  Official 
Journal. 

IN  THE  HIGH  COURT  OF  JUSTICE.  —  CHANCERY  DIVISION 

Before  MR.  JUSTICE  NEVILLE 

Feb.  20  — Mar.  18,  1913 

*  JOSEPH  CROSFIELD  &  SONS  LD.  v.  TECHNO-CHEMICAL 
LABORATORIES  LD. 

Patent.  —  Action  for  infringement.  —  Admissibility  of  expert  evi- 
dence. —  Construction  of  Specification.  —  Insufficiency  of  Specification 
-  Patent  held  invalid.  —  Action  dismissed.  —  Costs  on  the  higher  scale 
allowed. 

In  1903  a  Patent  was  granted  for  a  "  Process  for  converting  unsaturated 
"  fatty  acids  or  their  glycerides  into  saturated  compounds."  The  process 
consisted  in  treating  the  fatty  bodies  with  hydrogen  in  the  presence  of  a 
finely-divided  metal,  such  as  platinum,  iron,  cobalt,  copper,  and  espe- 
cially nickel,  adapted  to  act  as  a  catalyzer.  The  Specification  stated  that 
the  saturation  might  be  effected  by  causing  vapours  of  fatty  acid  together 
with  hydrogen  to  pass  over  the  catalytic  metal,  but  that  it  was  sufficient 
to  expose  the  fat  or  fatty  acid  in  a  liquid  condition  to  the  action  of  hydrogen 
and  the  catalyst.  The  Specification  gave  no  details  of  the  process,  but 
after  having  given,  in  general  terms,  an  example  of  the  process,  stated 
that  the  quantity  of  the  nickel  added  and  the  temperature  were  immaterial, 
and  would  only  affect  the  duration  of  the  process.  In  an  action  for  in- 
fringement of  the  Patent,  the  Plaintiffs  contended  that  the  publication  of 
the  fact  that  the  process  could  be  carried  out  with  bodies  in  the  liquid  state 

*  Supplement,  June  18,  1913.  The  Illustrated  Official  Journal  (Patents), 
Vol.  XXX.  Reports  of  Patent,  Design  and  Trade  Mark  Cases.  No.  12. 

301 


302  APPENDIX 

was  of  great  merit;  they  claimed  that  the  Patent  was  for  a  principle,  and 
that,  the  Patentee  having  shown  one  way  of  putting  it  .into  practice,  he 
was  entitled  to  claim  for  all  ways.  The  Defendants  contended  that  the 
experiments  of  their  witnesses  showed  that,  for  the  success  of  the  process, 
the  catalyst  must  be  prepared  in  a  particular  way  and  the  process  carried 
out  with  precautions  not  indicated  in  the  Specification  and  requiring 
research  for  their  ascertainment. 

Held,  that  the  Patentee  claimed  the  hydrogenation  of  all  unsaturated 
fatty  acids,  and  their  glycerides,  by  the  use  of  finely-divided  platinum, 
iron,  copper,  and  cobalt,  as  well  as  nickel,  and  that  if  the  process  failed 
as  to  any  of  the  bodies  to  be  hydrogenated  or  any  of  the  catalysts  the  Patent 
was  invalid;  that  no  method  of  carrying  the  alleged  invention  into  effect 
was  sufficiently  described  in  the  Specification;  and  that  the  Patent  was 
invalid.  The  action  was  dismissed  with  costs. 

On  the  21st  of  January  1903  Letters  Patent  (No.  1515  of  1903)  were 
granted  to  Wilhelm  Normann  for  a  "  Process  for  converting  unsatu- 
"  rated  fatty  acids  or  their  glycerides  into  saturated  compounds." 

The  Complete  Specification  was  as  follows:  —  "  The  property  of 
"  finely-divided  platinum,  to  exercise  a  catalytic  action  with  hydro- 
"  gen,  as  it  does  with  oxygen,  is  already  known.  For  instance,  Wilde 
"  observed  the  following  reaction  taking  place  in  the  presence  of 
"  platinum  black:  — 

"  C2H2  +  H4  =  CH3  -  CH3 

C2H4      |      tl2    =    Oils    —   Oils 

"  and  Debus  noticed  the  reaction: 

"  HCN  +  H4  =  CH3NH2 

"  Recently  Sabatier  and  Sender  ens  have  discovered  that  other 
"  finely-divided  metals  will  also  exercise  a  catalytic  effect  on  hydro- 
"  gen,  viz.  iron,  cobalt,  copper  and  especially  nickel.  By  causing 
"  acetylene,  ethylene,  or  benzene  vapour  in  mixture  with  hydrogen  gas 
"  to  pass  over  one  of  the  said  metals,  the  said  investigators  obtained 
"  from  the  unsaturated  hydrocarbons  saturated  hydrocarbons,  partly 
"  with  simultaneous  condensation. 

"  I  have  found,  that  it  is  easy  to  convert  by  this  catalytic  method 
"  unsaturated  fatty  acids  into  saturated  acids.  This  may  be  effected 
"  by  causing  vapours  of  fatty  acid  together  with  hydrogen  to  pass 
"  over  the  catalytic  metal,  which  is  preferably  distributed  over  a  suit- 
"  able  support,  such  as  pumice  stone.  It  is  sufficient,  however,  to 
"  expose  the  fat  or  the  fatty  acid  in  a  liquid  condition  to  the  action 
"  of  hydrogen  and  the  catalytic  substance.  For  instance,  if  fine  nickel 
"  powder  obtained  by  reduction  in  a  current  of  hydrogen,  is  added  to 


APPENDIX  303 

"  chemically  pure  oleic  acid,  then  the  latter  heated  over  an  oil  bath, 
"  and  a  strong  current  of  hydrogen  is  caused  to  pass  through  it  for 
"  a  sufficient  length  of  time,  the  oleic  acid  may  be  completely  con- 
"  verted  into  stearic  acid.  The  quantity  of  the  nickel  thus  added 
"  and  the  temperature  are  immaterial  and  will  only  affect  the  dura- 
"  tion  of  the  process.  Apart  from  the  formation  of  small  quantities 
"  of  nickel  soap,  which  may  be  easily  decomposed  by  dilute  mineral 
"  acids,  the  reaction  passes  off  without  any  secondary  reaction  taking 
"  place.  The  same  nickel  may  be  used  repeatedly.  Instead  of  pure 
"  oleic  acid,  commercial  fatty  acids  may  be  treated  in  the  same 
"  manner.  The  yellowish  fatty  acids  of  tallow,  which  melt  between 
"  44  and  48°  C.  and  whose  iodine  number  is  35.1,  will,  after  hydro- 
"  genation,  melt  between  56.5  and  59°  C.,  while  their  iodine  number 
"  will  be  9.8  and  their  colour  slightly  lighter  than  before,  and  they 
"  will  be  very  hard. 

"  The  same  method  is  applicable  not  only  to  free  fatty  acids,  but 
"  also  to  their  glycerides  occurring  in  nature,  that  is  to  say,  the  fats 
"  and  the  oils.  Olive  oil  will  yield  a  hard  tallow-like  mass;  linseed  oil 
"  and  fish  oil  will  give  similar  results. 

"  By  the  new  method,  all  kinds  of  unsaturated  fatty  acids  and  their 
"  glycerides  may  be  easily  hydrogenised.  It  is  not  necessary  to 
"employ  pure  hydrogen  for  the  purpose  of  the  present;  invention; 
"  commercial  gas  mixtures  containing  hydrogen,  such  as  water  gas, 
"  may  also  be  used." 

The  Patentee  claimed:  —  "  1.  The  process  for  converting  unsatu- 
"  rated  fatty  acids,  or  their  glycerides,  into  saturated  compounds, 
"  which  consists  in  treating  the  said  fatty  bodies  with  hydrogen  in  the 
"  presence  of  a  finely-divided  metal  adapted  to  act  as  a  catalyser, 
"  substantially  as  described.  2.  The  herein  described  manufacture 
"  of  saturated  fatty  compounds  from  unsaturated  fatty  acids,  or  their 
"  glycerides,  by  means  of  water  gas  or  similar  gas  mixtures." 

On  the  19th  of  December,  1911,  Joseph  Crosfield  &  Sons  Ld.  com- 
menced an  action  for  infringement  of  the  Patent  against  Techno- 
Chemical  Laboratories  Ld.  and  Nils  Testrup,  claiming  the  usual  relief. 

The  Plaintiffs  by  their  Statement  of  Claim  alleged  that,  (1)  they 
were  the  owners  of  the  Patent;  (2)  the  Patent  was  valid  and  subsisting; 
(3)  the  Defendants  had  infringed  and  threatened  and  intended  to 
infringe. 

By  their  Particulars  of  Breaches  they  alleged  that,  (1)  the  Defend- 
ants had  infringed  by  importing  into,  and  by  the  manufacture,  sale, 
offering  for  sale,  supply  and  use  in,  this  country  of  compounds  made 
in  accordance  with  the  process  described  in  the  Specification  and 


304  APPENDIX 

claimed  in  both  the  Claims,  and  by  the  use  in  this  country  of  the  proc- 
ess; and  (2),  in  particular,  the  Defendants,  and  each  of  them,  had, 
on  the  1st  of  December,  1911,  caused  to  be  treated  with  hydrogen  in 
the  presence  of  a  finely-divided  metal  adapted  to  act  as  a  catalyser, 
in  their  factory  situate  at  "  Fairlawn,"  Clapham  Park,  in  the  county 
of  London,  9  kilogrammes  of  cotton  oil,  in  infringement  of  both  the 
Claims. 

By  their  Defence  the  Defendants,  (1)  did  not  admit  the  allegations 
in  paragraph  1  of  the  Statement  of  Claim;  (2)  denied  that  they,  or 
either  of  them,  had  infringed  or  threatened  or  intended  to  infringe; 
and  (3)  said  that  the  Patent  was,  and  always  had  been,  null  and  void. 

By  their  amended  Particulars  of  Objections  they  said  that,  (1) 
Wilhelm  Normann  was  not  the  true  and  first  inventor.  (2)  The  alleged 
invention  was  not  subject-matter  for  a  valid  Patent,  by  reason  of  the 
common  and/or  public  knowledge  at  the  date  of  the  Patent.  The 
Defendants  would  refer  to  all  the  prior  publications  set  out  in  para- 
graph 4  below  as  disclosing  part  of  the  public  knowledge.  (3)  The 
alleged  invention  was  not  useful.  (4)  The  alleged  invention  had  been 
published  in  this  realm  prior  to  the  date  of  the  Patent :  —  (i)  By  the 
deposit  in  the  Patent  Office  Library  of  the  following  Specifications: 
(a)  British:  —  Lake  (No.  2798  of  1883)  and  Ramage  (No.  7242  of  1901). 
(6)  German:  —  Zurrer  (No.  62,407).  The  whole  of  each  of  the  Speci- 
fications was  relied  upon,  (ii)  By  the  sale  and  publication  in  the 
United  Kingdom,  and  by  the  deposit  in  the  Patent  Office  Library,  of 

(c)  "  Comptes  Rendus  de  TAcademie  des  Sciences,"  of  Paris,  vol.  133, 
dated   1901,   pages  321-4,   comprising  an  article  entitled   "  Chimie 
"  Organique.  —  Nouvelle  methode  de  preparation  de  1'aniline  et  des 
"  alcalis  analogues."     Note  de  MM.  Paul  Sabatier  et  /.  B.  Senderens. 

(d)  "Bulletin  de  la  Societe  de  Chimie,"  series  3,  vol.  1,  pages  295-6, 
comprising  a  communication  entitled  "  No.  29.  —  Transformation  de 
"  1'acide  oleique  en  acide  stearique  "  by  De  Wilde  and  Reychler.     (e) 
"  Journal  of  the  Chemical  Society,"  London,  for  the  year  1889,  vol. 
56,  part  2,  page  1140,  comprising  an  abstract  of  the  communication 
of  De  Wilde  and  Reychler.     (f)  "  Watts's  Dictionary  of  Chemistry," 
edition  1892,  vol.  3,  page  637,  column  2,  lines  42-4.     (g)  li  Sitzungs- 
"  berichte  der  Kaiserlichen  Akademie  der  Wissenschaften,"  Vienna, 
1876,  vol.  72,  part  II,  pages  366-75,  comprising  a  paper  by  Guido  Gold- 
schmiedt,   entitled   "  Uber  die  Umwandlung  von  Sauren  der  Reihe 
"  CnH2n-202  in  solche  der  Reihe  CnH2n02.     (5)  The  Complete  Speci- 
fication of  the  Patent  did  not  particularly  describe  and  ascertain  the 
nature  of  the  invention  and  in  what  manner  the  same  was  to  be  per- 
formed, and  was  insufficient  and/or  misleading  in  the  following  par- 


APPENDIX  305 

ticulars: —  (a)  No  useful  result  could  be  obtained  by  following  the 
directions  given  in  the  Specification.  (6)  No  process  was  described 
by  which,  as  alleged,  saturation  of  unsaturated  fatty  acids,  or  their 
glycerides,  could  be  easily  or  at  all  effected,  (c)  No  process  was  de- 
scribed by  which  fatty  acids,  or  their  glycerides,  could  be  hydroge- 
nised  by  the  action  of  catalytic  iron,  copper,  cobalt,  nickel  or  platinum. 
(d)  No  process  was  described  whereby  hydrogenation  of  fatty  acids, 
or  their  glycerides,  could  be  effected  without  the  formation  of  secondary 
products,  (e)  No  process  was  described  whereby  any  useful  results 
could  be  obtained  by  the  use  of  any  of  the  finely-divided  metals  men- 
tioned. (/)  No  process  was  described  whereby  fatty  acids,  or  their 
glycerides,  could,  as  suggested,  be  hydrogenised  by  treatment  in  a 
vaporised  condition,  (g)  The  treatment  as  described  of  oleic  acid  in 
the  liquid  condition  did  not  result  in  complete  saturation,  as  alleged, 
or  in  any  practical  or  substantially  useful  saturation,  (h)  No  suffi- 
cient directions  were  given  as  to  the  quality  of  catalyst,  or  the  tem- 
peratures or  times  required  to  produce  the  alleged  results,  or  as  to 
what  variations  of  those  factors  might  be  required  for  different  cata- 
lysts, and  those  factors  were  not  immaterial  as  to  the  alleged  results, 
(i)  The  same  catalyst  could  not  be  used  repeatedly  as  described  at 
page  2,  lines  40  to  41.  Alternatively,  no  sufficient  directions  were 
given  to  enable  the  same  catalyst  to  be  used  repeatedly,  (j)  No  useful 
result  could  be  obtained  by  the  use  of  commercial  gas  mixtures  as 
described  on  page  3,  lines  5  and  6.  (k)  No  sufficient  directions  were 
given  as  to  the  preparation  of  nickel  or  other  metal  to  be  used  as 
catalyst.  (I)  The  statement  on  page  3,  lines  3  and  4,  of  the  Specifica- 
tion, namely,  that  by  the  new  method  all  kinds  of  unsaturated  fatty 
acids  and  their  glycerides  might  be  easily  hydrogenised,  was  incorrect. 
(m)  No  sufficient  directions  were  given  as  to  which  impurities  might 
be  present  with,  or  as  to  which  impurities  must  be  excluded  from,  the 
hydrogen  in  order  that  the  process  might  be  carried  out. 

By  their  further  and  better  Particulars  the  Defendants  alleged  that 
as  to  paragraph  5  (I)  of  their  Particulars  of  Objections,  the  following 
would  not  be  easily  or  at  all  hydrogenised:  —  Olive,  linseed,  fish, 
whale,  rape,  and  cottonseed  oils,  or  any  fatty  oils;  oleic,  erucic,  linolic, 
linoleic,  and  ricinoleic  acids,  or  any  unsaturated  fatty  acids,  by  treat- 
ment in  a  vaporised  or  liquid  condition  by  the  alleged  new  method. 
And  they  alleged  as  to  paragraph  5  (m)  that  the  following  impurities 
must  be  excluded  from  the  hydrogen  in  order  that  the  latter  could,  by 
any  process,  hydrogenise  fatty  acids  or  their  glycerides:  —  Sulphur, 
sulphuretted  hydrogen,  and  all  other  volatile  sulphur  compounds, 
arsenic,  arseniuretted  hydrogen  and  all  other  volatile  arsenic  com- 


306  APPENDIX 

pounds,  phosphorus,  phosphoretted  hydrogen  and  all  other  volatile 
phosphorus  compounds,  chlorine,  oxygen,  the  oxides  of  nitrogen, 
ammonia,  and  empyreumatic  substances  obtained  in  the  production 
of  water  gas. 

Upon  an  application  by  the  Plaintiffs  for  further  and  better  Particu- 
lars as  to  paragraph  5  (7),  the  Defendants  alleged  that  no  fatty  oils 
and  no  unsaturated  fatty  acid  could  be  easily  or  at  all  hydrogenised 
in  a  vaporised  or  liquid  condition  by  the  Plaintiffs'  process,  and  stated 
that  they  did  not  intend  to  offer  any  evidence  of  specific  instances 
other  than  those  specified  in  the  Particulars. 

In  their  Answers  to  Interrogatories  the  Defendant  Company  stated 
that,  on  the  occasion  of  the  visit  of  the  Patentee  to  the  Defendant 
Company's  premises  at  Fairlawn,  Clapham  Park,  on  the  1st  of  De- 
cember, 1911,  to  inspect  a  process  for  the  hardening  of  fats,  there  was 
used  a  cylindrical  autoclave  1  metre  high  and  f  metre  in  diameter 
(inside  measurements),  with  a  steam  jacket,  and  fitted  with  a  non- 
conducting lining  of  unknown  material.  Nine  kilograms  of  cotton  oil 
were  pumped  into  the  autoclave,  and  288  grams  of  a  composition, 
containing  a  catalytic  agent  calculated  on  the  oil,  was  used  and  was 
mixed  with  the  oil  prior  to  the  introduction  of  the  mixture  into  the 
autoclave.  The  autoclave  was  then  filled  with  hydrogen  from  a 
cylinder  to  a  pressure  of  15  atmospheres.  During  the  operation,  the 
pressure  varied  from  time  to  time  according  to  the  absorption  of 
hydrogen.  A  mechanically  driven  circulation  pump  was  connected 
with  the  autoclave  both  by  its  suction  and  delivery  conduits.  By 
means  of  a  pump  and  a  jet  for  spraying,  a  mixture  of  oil  and  composi- 
tion containing  the  catalytic  agent  was  drawn  from,  and  forced  back 
into,  the  autoclave.  The  iodine  absorption  was  not  determined.  The 
composition  containing  the  catalytic  agent  was  prepared  from  a  salt 
of  nickel.  The  Defendant  Company  said  that  the  catalyst  was  the 
subject  of  provisional  protection  (No.  4702  of  1912),  and  they  ob- 
jected to  giving  further  particulars,  but  subsequently  they  said  that 
the  composition  was  prepared  as  follows:  —  About  1J  kilograms  of 
nickel  sulphate  was  dissolved  in  about  3  litres  of  water,  and  about  the 
same  weight  of  sodium  carbonate,  dissolved  in  about  the  same  quan- 
tity of  water,  and  at  about  70-80°  C.,  was  added  to  the  nickel  sulphate 
which  was  at  about  60-70°  C.  The  mixture  was  stirred  for  about 
1J-2  hours,  and  the  precipitate  was  filtered  off  and  washed  with  dis- 
tilled water  at  about  25°  C.  for  60-70  hours  alternately  in  tanks  and 
filter  press.  A  small  sample  was  dried  and  tested  to  ascertain  that 
the  precipitate  had  been  sufficiently  washed.  The  washed  precipitate 
was  dried  in  hot  air  at  80-85°  C.,  and  was  calculated  to  weigh  720 


APPENDIX  307 

grams.  It  was  then  roasted  in  an  iron  frying  pan  for  about  15  minutes 
over  an  open  Bunsen  gas  burner,  and  the  weight  after  roasting  was 
calculated  to  be  about  380  grams.  The  product  was  heated  to  about 
300°  C.  for  about  6  minutes  in  a  current  of  hydrogen  in  revolving  glass 
tubes  slightly  inclined,  the  precipitate  being  introduced  at  the  higher 
end  and  through  a  spiral  glass  tube,  and  the  hydrogen  at  the  lower  end. 
The  product,  which  weighed  288  grams,  was  directly  introduced  into  a 
small  quantity  of  oil,  which  was  mixed  with  the  9  kilos  the  following 
day. 

The  Defendants  during  the  trial  referred  to  the  following  papers:  - 
Moissan,  Oxides  of  nickel  ("  Annales  de  chimie  et  de  physique,"  1880, 
5th  series,  vol.  21,  page  238)  —  the  exhibit  A.L.  9;  Moissan  and 
Moureu,  Action  of  acetylene  on  iron,  &c.  ("  Comptes  Rendus,"  1896, 
vol.  122,  1st  half  year,  page  1240)  —  the  exhibit  A.L.  9;  Sabatier  and 
Senderens  in  the  "Comptes  Rendus"  (the  exhibit  A.L.  5),  Action  of 
nickel  on  ethylene  (124  (1897),  page  616);  Action  of  nickel  on  ethyl- 
ene:  synthesis  of  ethane  (ib.,  page  1358);  Hydrogenation  of  acetylene 
in  the  presence  of  nickel  (128  (1899),  page  1173);  Action  of  copper  on 
acetylene;  formation  of  a  very  condensed  hydrocarbon,  cuprene  (130 
(1900),  page  250);  Hydrogenation  of  acetylene  in  the  presence  of 
copper  (ib.,  page  1559);  Hydrogenation  of  acetylene  in  the  presence 
of  reduced  iron  or  cobalt  (ib.,  page  1628);  Hydrogenation  of  ethylene 
in  the  presence  of  various  reduced  metals  (ib.,  page  1761);  Hydro- 
genation of  acetylene  and  ethylene  in  the  presence  of  divided  platinum 
(131  (1900),  page  40);  Action  of  various  divided  metals,  platinum, 
cobalt  and  iron,  on  acetylene  and  ethylene  (ib.  (1900),  page  267); 
Direct  hydrogenation  effected  in  the  presence  of  reduced  nickel ;  prepa- 
ration of  hexahydrobenzene  (132  (1901),  page  210);  General  method  of 
synthesis  of  the  naphthenes  (ib.  (1901),  page  566);  Hydrogenation  of 
various  aromatic  hydrocarbons  (ib.,  page  1254);  new  method  of  pre- 
paring aniline  and  analogous  alkalies  (133  (1901),  page  321);  direct 
hydrogenation  of  carbon  oxides  in  the  presence  of  various  divided 
metals  (134  (1902),  page  689);  Hydrogenation  of  ethylenic  hydro- 
carbons by  the  contact  method  (ib.,  page  1127);  Synthesis  of  various 
petroleums:  contribution  to  the  theory  of  the  formation  of  natural 
petroleums  (ib.,  page  1185);  Direct  hydrogenation  of  acetylenic  hydro- 
carbons by  the  contact  method  (135  (1902),  page  87);  Direct  hydro- 
genation of  oxides  of  nitrogen  by  the  contact  method  (ib.,  page  278) ; 
and  a  paper  by  the  same  authors  in  the  "Annales  de  chimie,"  &c.,  8th 
series,  vol.  4  (1905),  page  5  —  an  exhibit  marked  J.L.  1. 

Sir  A.  Cripps  K.C.  for  the  Plaintiffs.  —  The  Plaintiffs  are  substan- 
tially Brunner,  Mond  &  Co.,  and  the  real  Defendants  are  Lever  Bros. 


308  APPENDIX 

Ld.  An  important  feature  of  the  invention  is  that  it  has  enabled  fish 
oils,  and  particularly  whale  oil,  to  be  used  for  soap-making,  hardening 
it  and  destroying  its  smell.  Before  the  Patent,  it  was  not  known  that 
the  catalytic  hydrogenation  of  fatty  acids  or  oils  could  be  effected 
without  alteration  of  the  quantity  of  oxygen  contained  in  the  acids  or 
oils.  The  Patentee  did  not  discover  any  new  method  of  using  catalysts, 
but  he  used  them  successfully  with  bodies  with  which  they  had  never 
been  used  before;  and  he  found  that  catalysts  could  be  used  with  sub- 
stances, that  could  not  be  readily  vaporised,  by  simply  treating  them 
in  the  liquid  state.  That  had  been  thought  impossible.  It  is  alleged 
that  the  directions  given  in  the  Specification  are  insufficient,  but  the 
Patent  is  for  a  principle  of  wide  scope  and  there  is  no  need  for  minute 
directions,  because  the  process  will  work  under  all  conditions.  The 
invention  has  effected  a  revolution  in  the  soap-making  industry,  and 
the  Patent  is  a  master  Patent.  The  Specification  describes  a  way  of 
putting  the  principle  into  practice.  Lake's  Specification  deals  merely 
with  the  extraction  of  glycerine  from  fatty  substances,  and  has  no  bear- 
ing on  the  invention  here;  nor  has  Ramage's  Specification,  which 
relates  only  to  the  drying  of  oils,  without  any  hydrogenation.  Zurrer's 
process  is  merely  for  saturating  fatty  acids  with  chlorine,  and  then 
replacing  the  chlorine  by  hydrogen  by  heating  under  pressure  with 
water  and  metals ;  there  is  no  catalytic  action.  Sabatier  and  Senderens 
state  generally  the  catalytic  action  of  certain  finely-divided  metals  in 
adding  hydrogen  to  incomplete  organic  molecules,  and  then  go  on  to 
deal  with  the  substitution  of  hydrogen  for  oxygen.  The  Patentee's 
object  is  to  keep  the  oxygen  in  the  acids  and  oils,  and  to  add  hydrogen, 
and  Sabatier  would  lead  people  away  from  that.  The  papers  by  De 
Wilde  and  Reychler  and  Goldschmiedt  do  not  deal  with  catalytic  proc- 
esses at  all.  The  Defendants  allege  non-utility,  meaning  that  if  the 
Patentee's  directions  are  followed  the  result  that  he  describes  would 
not  be  obtained.  Several  of  the  allegations  in  paragraph  5  of  the 
Particulars  of  Objections  are  mere  general  allegations  that  the  Paten- 
tee's process  will  not  work.  Catalytic  action  was  well  known,  and  it 
was  not  necessary  to  give  directions  as  to  the  mode  of  preparation  of 
the  catalysts.  The  claim  is  for  the  application  of  known  catalytic 
methods  to  substances  to  which  they  had  not  been  applied  before  — 
for  obtaining  an  old  ^product  by  a  new  method.  The  Patentee  men- 
tions nickel  as  a  catalyst,  as  being  the  best  metal  for  the  purpose.  A 
competent  chemist  would  have  no  difficulty  in  finding  what  were  the 
best  temperatures  and  proportions. 

Evidence  was  given  in  support  of  the  Plaintiffs'  case. 

Dr.  A.  Liebmann  stated  that  fats  could  not  be  vaporized.     There 


APPENDIX  309 

was  nothing  in  literature  as  to  anyone,  prior  to  the  date  of  the  Patent, 
having  acted  with  hydrogen  as  a  catalyzer  on  a  liquid;  Sabatier  had 
said  the  presence  of  the  liquid  was  fatal  and  destroyed  the  catalyst. 
The  liquid  oils,  after  having  been  hardened  and  made  into  fats  by 
the  patented  process,  could  be  used  for  various  purposes.  In  the 
case  of  the  fish  oils  the  disagreeable  smell  was  destroyed,  and  cheap 
vegetable  oils  could  be  used  for  the  manufacture  of  margarine,  and 
oils  could  be  rendered  useful  for  soap-making  or  candle-making.  Be- 
fore 1903  it  was  known  that  it  was  impossible  to  obtain  a  vapour  of 
a  glyceride,  and  that  a  fatty  acid  could  be  distilled  in  super-heated 
steam,  or  under  reduced  pressure.  Steam  would  probably  oxidise 
the  catalyst  unless  hydrogen  was  present,  and  it  would  be  excluded 
from  vaporisation.  The  witness  had  used  a  current  of  hydrogen  for 
the  vaporisation  of  fatty  acids.  He  gave  details  of  experiments  he 
had  successfully  made  in  the  application  of  the  patented  process. 

Dr.  F.  W.  Passmore  stated,  inter  alia,  that  the  great  part  of  the 
invention  was  that  it  had  shown  the  erroneous  character  of  the  old 
theory  that  anything  that  would  tend  to  cover  up  the  surface  of  the 
catalyst  would  destroy  it,  and  had  shown  that  it  was  possible  to 
catalyse  in  fat. 

Sir  James  Dewar  also  gave  evidence. 

Walter  K.C.  summed  up  the  Plaintiffs'  case.  —  Moissan  and  Moureu 
in  1896  dealt  with  the  action  on  a  mixture,  of  acetylene  and  hydro- 
gen, of  iron,  nickel  and  cobalt  prepared  by  reduction  with  hydrogen 
at  as  low  a  temperature  as  possible.  They  found  that,  when  incan- 
descence took  place,  part  of  the  acetylene  was  polymerised,  and  part 
was  split  up.  Their  theory  was  that  the  porous  state  of  the  metal 
led  to  the  condensation  of  the  acetylene,  and  the  evolution  of  heat, 
and  that  all  bodies  having  that  catalytic  or  pyrophoric  structure 
must  give  an  identical  result.  They  referred,  as  to  the  precautions 
to  be  taken  in  obtaining  the  nickel,  to  the  paper  by  Moissan  in  the 
"  Annales  de  Chimie,"  1880.  Dr.  Passmore  said  that  he  found  in- 
structions to  obtain  the  hydrated  oxide  of  nickel  in  a  finely-divided 
state  by  precipitation  from  the  nitrate,  sulphate,  or  carbonate,  and 
that  the  finely-divided  nickel,  obtained  from  that  oxide  by  reduction 
at  as  low  a  temperature  as  possible,  would  be  pyrophoric  and  de- 
compose acetylene.  Sabatier  and  Senderens  continued  Moissan's 
work,  and,  in  their  Papers  on  the  action  of  nickel  on  ethylene,  said 
that  the  reaction  takes  place  with  the  catalytic  nickel,  with  nickel 
reduced  at  a  red  heat,  or  even  with  nickel  filings.  Then  they  dealt  with 
the  conversion  of  ethylene  into  ethane  by  means  of  hydrogen  and  a 
catalytic  agent.  After  that,  they  dealt  with  the  hydrogenation  of 


310  APPENDIX 

acetylene  in  presence  of  nickel,  and  with  the  action  of  copper  and  of 
iron  and  cobalt  on  acetylene,  and  with  the  hydrogenation  of  ethylene 
in  presence  of  various  reduced  metals,  with  the  hydrogenation  of 
benzene,  and  with  the  preparation  of  aniline  from  nitro-benzene  and 
analogous  nitro-bodies.  The  results  show  that  it  is  impossible  to 
say  that  the  method  that  will  act  in  some  cases  will  act  in  others,  or 
to  see  why  the  fatty  acids  do  not  wet  or  act  upon  the  surface  so  as 
to  inhibit  the  action  of  the  catalyst.  Nowhere  throughout  those 
Papers  is  there  any  work  with  other  than  pyrophoric  bodies,  except 
in  the  case  of  acetylene  and  ethylene.  Normann  continued  the 
work.  He  referred  to  the  literature  telling  how  to  prepare  the  cata- 
lysts, although  he  need  not  have  done  so,  as  the  literature  was  part 
of  the  common  stock  of  knowledge  of  chemists.  He  stated  that  the 
fatty  acids,  not  their  glycerides,  may  be  treated  in  the  vaporised 
condition.  There  is  no  mystery  as  to  the  method  of  converting  them 
into  vapours.  It  is  a  common  operation  to  bubble  hydrogen  through 
a  liquid,  and  get  the  vapour  of  the  liquid  mixed  with  hydrogen.  And 
Sabatier  described  that  method,  and  also  the  use  of  a  capillary  tube. 
Then  came  Normann's  great  discovery,  that  the  fatty  acids,  and  their 
glycerides,  could  be  treated  in  the  liquid  condition.  The  explanation 
seems  to  be  that  the  liquid  does  not  wet  the  metal,  just  as  oil  will 
stick  to  metal  and  not  to  rock,  and  so  float  up  the  metal.  As  to  the 
use  of  an  oil-bath,  that  appliance  is  used  when  the  temperature  de- 
sired is  from  about  100°  to  250°.  All  the  experiments  conducted  at 
temperatures  between  these  limits  succeeded.  No  chemist  would 
endeavour  to  obtain  finely-divided  nickel  by  first  grinding  the  oxide. 
In  some  of  the  Defendants'  experiments  the  oxide  from  which  the 
nickel  was  obtained  was  ground;  it  ought  to  have  been  precipitated  — 
grinding  will  not  give  the  fineness  required. 

Asibury  K.C.  for  the  Defendants.  —  The  precipitated  oxide  dries 
into  a  hard  cake,  that  has  to  be  ground.  There  is  no  evidence  that 
Normann's  process  is  useful.  The  solidification  of  oils  in  this  coun- 
try is  only  now  coming  into  commercial  use.  An  ordinary  chemist 
might  work  on  Normann's  process  for  years,  and  obtain  no  useful 
result  at  all.  The  Specification  is  deficient  as  to  any  valuable  direc- 
tions, and  is  misleading.  To  obtain  a  useful  result  something  must 
be  done  that  is  not  even  hinted  at  in  the  Specification  or  in  Sabatier1  s 
papers.  A  catalyst  that  will  work  with  one  sample  of  some  particu- 
lar fatty  acid  or  glyceride  will  not  work  with  another  sample.  The 
whole  matter  is  mysterious.  Sabatier  did  not  use  the  pyrophoric 
metal  used  by  Moissan,  and  the  Specification  ought  to  have  given 
directions  on  the  point.  The  Specification  may  be  construed  as 


APPENDIX  311 

saying  that  fats  may  be  treated  in  the  vaporised  state,  though  it  is 
sufficient  for  them  to  be  treated  in  the  liquid  condition;  and  it  is  ad- 
mitted that  fats  cannot  be  vaporised.  The  nickel  used  by  the  De- 
fendants has  been  obtained  by  the  ordinary  process  of  reduction  in 
hydrogen,  and,  if  that  is  not  sufficient,  the  Patent  is  invalid  for  in- 
sufficiency of  the  Specification.  The  Patentee  says  the  temperature 
is  immaterial,  but  no  one  has  used  a  temperature  below  100°,  and 
some  of  Sabatier's  processes  take  place  in  the  cold.  If  Normann  had 
tried  besides  nickel,  iron,  cobalt,  and  copper,  he  would  have  found 
out  certain  differences  between  their  action  and  that  of  nickel,  and 
in  that  case  he  ought  to  have  disclosed  the  best  method  of  carrying  out 
the  process.  He  says  that  water-gas  may  be  used;  that  means  com- 
mercial water-gas,  which  contains  sulphuretted  hydrogen  and  cannot 
be  successfully  used.  The  Claim  is  for  applying  catalysis  to  the  fatty 
bodies  by  vaporising  or  by  the  liquid  process.  The  Plaintiffs'  wit- 
nesses state  that  if  one  makes  reduced  nickel  by  the  processes  described 
in  the  text-books  one  will  fail,  and  Dr.  Liebmann  went  so  far  as  to  say 
that  one  would  probably  fail  if  one  bought  nickel  oxide  in  a  shop  and 
reduced  it  as  told  by  Sabatier.  The  Plaintiffs  say  their  case  stands  or 
falls  on  being  able  to  confine  their  Patent  to  preparing  the  catalyst 
by  the  particular  method  described  in  Sabatier's  and  Moissan's  papers. 
But  Moissan  describes  the  reduction  of  the  hydrated  sesquioxide  of 
nickel  obtained  by  the  action  of  chlorine  on  the  hydrate  of  nickel 
protoxide  and  neither  Sabatier  nor  Normann  suggests  that  it  is  neces- 
sary to  use  the  oxide  prepared  in  that  way.  The  use  of  chlorine 
would  "  poison  "  the  catalyst.  The  Plaintiffs  say  that  the  nickel,  to 
be  catalytic,  must  be  pyrophoric,  but  pyrophoric  nickel  will  hot  act 
in  some  cases.  For  some  unexplained  reason,  it  will  harden  one 
sample,  say,  of  linseed  oil,  but  not  another  sample.  The  action  de- 
pends on  the  mode  of  preparation  of  the  body  from  which  the  oxide 
is  made,  on  something  in  the  fatty  body,  and  on  the  temperature. 
Sabatier  is  actually  misleading,  as  he  did  not  say  that  it  is  material 
how  the  oxide  is  made,  and  he  did  not  say  anything  about  the  mode 
of  preparing  the  bodies  from  which  the  oxide  is  obtained.  Mr.  Bal- 
lantyne  followed  Normann,  Sabatier,  and  Moissan  and  failed  in  every 
case.  Then  he  had  a  suggestion  from  the  Defendant  Testrup,  not 
given  by  the  Plaintiffs'  authorities,  and  in  some  cases  he  succeeded 
and  in  some  he  failed.  He  had  found  a  similar  result  in  repeating 
Dr.  Passmore's  experiments.  Iron  with  acetylene  is  very  pyrophoric, 
but  iron  as  a  catalyst  for  hydrogenation  is  practically  useless;  it  will 
not  act  at  all  with  liquids.  The  temperature  at  which  the  catalyst 
is  prepared  is  immaterial  except  as  to  acetylene.  Sabatier  said  that 


312  APPENDIX 

the  catalytic  decomposition  of  ethylene  takes  place  very  well  if  the 
nickel  has  been  reduced  at  a  red  heat,  and  in  that  case  it  is  not 
pyrophoric.  But  the  nickel  is  not  so  active  as  if  it  had  been  reduced 
at  300°,  which  is  not  Moissan's  temperature.  A  chemist  reading 
Sabatier's  Papers  would  conclude  that  the  density  of  the  nickel  is  not 
increased  by  higher  temperature,  whether  it  is  partly  in  the  reduction 
or  in  the  next  process.  Sabatier  says  the  nickel  must  be  freshly  re- 
duced; the  Defendants  have  always  freshly  reduced  theirs.  He  says 
that  acetylene  can  be  hydrogenised  by  sheet  copper.  There  is  not  a 
single  suggestion  in  Sabatier's  Papers  that  one  is  to  reduce  from  a 
hydrate,  and  from  a  body  that  itself  has  been  prepared  at  a  low  tem- 
perature, and  still  less  is  there  any  suggestion  that  the  temperature 
of  reduction  in  any  case  should  be  Moissan's  240°,  instead  of  300°. 
The  Specification  is  capable  of  being  construed  as  meaning  that  the 
vapour  process  is  applicable  to  the  fats  as  well  as  to  the  fatty  acids, 
that  the  expression  "  fatty  acids,"  when  used  alone,  stands  both  for 
the  acids  and  their  glycerides,  the  fats.  The  Patentee  either  knew, 
or  did  not  know,  that  Sabatier's  method  would  not  act,  that  it  was 
necessary  to  adopt  Moissan's  method  of  reduction  from  a  higher 
oxide  at  a  low  temperature,  and  that  the  hydrate,  instead  of  the 
oxide,  must  be  used.  If  he  knew  any  one  of  those  three  matters, 
which  are  essential  to  success,  he  has  not  mentioned  them;  if  he  did 
not  know  them,  then  he  has  not  made  an  invention.  And,  even  if 
the  catalyst  is  prepared  by  the  Plaintiffs'  method,  with  certain  of  the 
fats  and  fatty  bodies,  no  result  is  obtained.  To  infringe  a  master 
Patent  by  the  use  of  an  equivalent,  the  equivalent  must  be  known  at 
the  date  of  the  Patent  to  be  an  equivalent.  In  1903  it  was  not  known 
that,  in  acting  catalytically  on  a  liquid,  it  was  equivalent  to  bubbling 
hydrogen  through  the  liquid  to  take  a  fatty  body  and  the  metal  and 
spray  them  into  a  chamber  containing  hydrogen  under  pressure,  for 
it  is  admitted  that  no  catalysis  of  a  liquid  was  known  at  all,  and  none 
of  the  witnesses  knew  of  any  process,  catalytic  or  other,  in  which  the 
metal  and  body  were  sprayed  together,  or  any  liquid  with  metal  in 
suspension  in  it  was  sprayed  into  a  gas  under  pressure.  That  is  an 
invention  of  Testrup,  and  will  give  results  that  the  Patentee's  process 
will  not  give.  The  Patentee  says  that  temperatures  are  unimportant ; 
Sabatier  says  they  are  most  important;  they  vary  greatly  with  each 
catalyst  and  body  acted  on;  it  is  impossible  to  get  any  general  law 
out  of  Sabatier  at  all.  There  is  no  evidence  that  the  patented  process 
has  ever  been  worked. 

Evidence  was  given  in  support  of  the  Defendants'  case. 

H.  Ballantyne,  in  answer  to  questions  dealing  with  the  point  whether 


APPENDIX  313 

a  chemist  would  know  that  by  obtaining  nickel  oxide  through  the 
hydroxide  by  precipitation,  he  would  get  the  oxide  in  a  more  porous 
form,  stated  that  a  chemist  could  get  the  oxide  in  a  bulky  but  finely- 
divided  state,  and  that  he  would  know  that  he  would  have  a  more 
finely-divided  material  than  if  he  went  to  a  higher  temperature.  The 
witness  said  that,  as  to  specimens  of  nickel  reduced  from  the  oxide 
and  nickel  reduced  from  the  carbonate,  the  latter  would  be  more 
bulky,  and  more  finely-divided,  but  would  have  a  larger  particle; 
the  two  specimens  could  both  be  sufficiently  rapidly  permeated  by  a 
gas,  and  the  denser  of  the  two  would  have  better  pyrophoric  proper- 
ties than  the  other,  but  pyrophoric  activity  was  independent  of  cata- 
lytic activity;  in  the  case  of  the  hydrogenation  of  oil  one  is  dealing 
with  a  liquid  getting  into  a  porous  body.  When  the  nickel  oxide  was 
reduced,  nickel  would,  by  the  removal  of  the  oxygen,  be  left  in  a 
cavernous  condition,  though  there  might  be  some  contraction. 

0.  Hehner  stated,  that  he  had  made  a  series  of  experiments  —  in 
which  he  used  the  purest  oleic  acid,  and  2  per  cent  of  the  most  active 
nickel  reduced  at  360°  from  purest  nickel  oxide  for  three  hours.  The 
rate  of  hydrogen  flow  was  about  14  litres  per  hour,  and  the  depth  of 
the  oil  column  4  inches  and  the  width  If  inches.  The  temperatures 
throughout  the  respective  experiments  were  90°,  100°,  120°,  and  150°. 
The  original  iodine  absorption  was  86.4  per  cent.  After  18  hours 
10  minutes,  it  was  reduced  in  experiment  (3)  to  85.1  and  in  (4)  to 
81.7,  in  (5)  to  82.9,  and  in  (6)  to  61.8;  and  in  the  last  experiment,  after 
57  hours  5  minutes,  it  was  reduced  to  45.5. 

Dr.  Julius  Lewkowitsch  stated,  that  before  1903  he  had  read 
Sabatier's  earlier  Papers  and  had  tried  to  hydrogenate  oleic  acid,  as 
vapour  and  as  liquid,  with  nickel;  but  had  failed.  He  had  prepared 
the  nickel  by  converting  the  sulphate  into  carbonate,  converting  that 
into  oxide,  and  reducing  the  oxide  at  400°  or  a  little  above.  Then  he 
had  read  the  Specification,  but  had  again  failed.  Later  he  had  read 
Sabatier's  Paper  of  1905  and  had  succeeded  after  two  years'  work. 

0.  Hehner,  recalled,  stated,  that,  in  preparing  the  nickel  he  used, 
he  had  made  the  green  hydroxide,  and  treated  it  with  chlorine,  obtain- 
ing Moissan's  sesquioxide. 

Dr.  A.  Liebmann,  recalled,  stated  in  cross-examination,  that  he 
had  made  a  number  of  further  experiments.  For  one,  he  had  bought 
nickel  protoxide,  reduced  it  at  300°-320°  C.,  and  used  it  for  the 
hydrogenation  of  oleic  acid  and  had  succeeded. 

Jenkins  K.C.  summed  up  the  Defendants  case.  —  The  Patent  is 
invalid,  first,  because  the  Patentee  claims  a  process  for  converting 
unsaturated  fatty  acids  into  saturated  compounds  by  a  catalytic 


314  APPENDIX 

method  applied  to  the  vapours  of  the  fatty  acids,  which  process  is  not 
useful;  secondly,  because  he  claims  a  process  for  converting  unsat- 
urated  fatty  acids,  or  their  glycerides,  into  saturated  compounds  by 
a  catalytic  method  applied  to  the  vapours  of  the  glycerides,  which 
process  is  impossible;  thirdly,  because  he  claims  the  substitution  of 
commercial  gas  mixtures  for  hydrogen  in  carrying  out  his  processes, 
whereas  the  use  of  those  gas  mixtures  renders  the  processes,  if  other- 
wise practicable,  impracticable  unless  the  mixtures  are  purified,  and 
he  gives  no  directions  for  their  purification;  fourthly,  because  he 
claims  a  catalytic  method  wherein  metals  other  than  nickel,  and  par- 
ticularly iron,  cobalt,  copper,  and  platinum,  are  employed  as  the 
catalysers,  which  processes  are  impossible  or  impracticable;  or,  alter- 
natively, the  Specification  is  insufficient  and  misleading  in  that  no 
sufficient  directions  are  given  as  to  the  catalytic  substance  necessary 
to  be  employed  to  enable  the  invention  to  be  carried  out;  and,  fifthly, 
because  the  Specification  is  insufficient  in  that  no  sufficient  directions 
are  given  to  enable  the  invention  to  be  performed  so  far  as  the  same 
relates  to  the  processes  claimed  for  the  conversion  of  unsaturated 
fatty  acids  or  their  glycerides  in  a  liquid  condition  into  saturated  com- 
pounds. The  first  four  reasons  depend  to  a  great  extent  upon  con- 
struction, and  do  not  involve  much  dispute  as  to  facts.  If  any  one  of 
them  is  valid,  it  is  possible  that  the  Patent  might  be  made  good  by 
amendment,  but  if  the  fifth  reason  —  the  broad  attack  —  is  valid 
then  the  Patent  could  not  be  made  good  by  any  amendment.  If  the 
Defendants  succeed  on  any  one  of  these  points  they  are  entitled  to 
have  the  action  dismissed.  The  first  objection  assumes,  for  the  pur- 
pose of  argument,  that  the  Specification  tells  how  the  process  can  be 
carried  out,  but  asserts  that  when  carried  out  it  is  useless.  As  to  the 
vapour  process,  the  Patentee  seemed  not  to  know  that  the  fats  cannot 
be  vaporized,  as,  in  1912,  he  applied  for  a  Patent  in  the  Transvaal 
and  said  in  his  Declaration  that  the  glycerides  might  be  exposed  in  a 
vaporised  condition  to  the  action  of  the  hydrogen  and  catalyst.  With 
regard  to  the  use  of  commercial  gas,  which  is  the  subject  of  a  separate 
Claim,  Sabatier  removed  the  sulphuretted  hydrogen  that  would  be  fatal 
to  the  process,  but  the  Patentee  gives  the  impression  that  purifica- 
tion is  not  necessary.  The  Defendants  have  shown  that  one  cannot, 
by  using  iron,  cobalt,  copper  or  platinum  as  catalysts,  bring  about 
the  hydrogenation.  The  Plaintiffs'  witnesses  say  that  they  have 
effected  the  hydrogenation  with  iron,  cobalt  and  copper  in  the  vapour 
process;  but  the  Defendants  have  shown  that  one  cannot  succeed 
with  these  metals  or  platinum  in  the  liquid  process.  If  the  Patentee 
claims  hydrogenation  in  the  liquid  process  by  a  metal  other  than  nickel, 


APPENDIX  315 

the  Patent  is  invalid.  With  regard  to  platinum  black,  the  Plaintiffs 
have  not  shown  that  it  will  work  with  anything.  They  say  that  it  is 
not  material,  that  is  a  question  of  construction;  and  the  Defendants 
say  that  the  Claim  includes  finely-divided  platinum.  As  to  the  gen- 
eral scope  of  the  Specification,  the  expression  "  this  catalytic  method  " 
means  the  use  of  the  finely-divided  metals  to  exercise  a  catalytic 
action  with  hydrogen  as  they  did  with  oxygen.  The  Plaintiffs  seemed 
to  think  that  Sabatier's  Papers  were  to  be  treated  as  if  the  Patentee 
had  recited  them,  but  that  is  a  false  construction.  He  did  not  recite 
them,  but  he  recited  prior  knowledge  so  far  as  was  known  to  him,  and 
exhaustively,  as  he  mentions  platinum  black,  and  makes  it  clear  that 
he  may  include  platinum  sponge.  Then  he  gives  general  directions 
that  it  is  sufficient  to  expose  the  fat  or  fatty  acid,  in  a  liquid  condition, 
to  the  action  of  hydrogen  and  the  catalytic  substance.  That  is  the 
Patentee's  claim.  It  is  not  narrowed  by  what  follows.  The  Patentee 
has  thrown  his  net  very  widely,  and  has  taken  a  correspondingly 
heavy  burden.  He  thought  he  had  discovered  a  new  principle,  and 
had  found  that  the  supposed  capriciousness  of  catalytic  action  did 
not  exist.  The  Plaintiffs  have  been  working  on  this  subject  for  years, 
but  they  have  not  told  the  Court  what  they  have  been  doing.  It  is 
difficult  to  avoid  reading  their  subsequently-acquired  knowledge  into 
the  knowledge  of  1903.  It  may  be  said  that  the  Patentee  has  pre- 
scribed, in  a  loose  way,  a  range  of  temperature  from  100°  to  250°  — 
the  range  of  an  ordinary  oil-bath ;  but  he  has  stated  that  the  reaction 
will  be  obtained  at  100°  with  every  body  treated.  And,  as  he  says 
that  temperature  is  immaterial,  he  has  not  purported  to  give  any  range 
of  temperature.  The  Plaintiffs  have  to  choose  between  saying  that 
the  statement  that  temperature  is  immaterial  is  of  general  application, 
in  which  case  the  Patent  is  clearly  bad,  and  saying  that  the  direction 
merely  refers  to  the  instance  given,  of  nickel,  and  that  the  statement 
means  that  having  found  a  temperature  at  which  the  reaction  is 
obtained,  it  is  immaterial  whether  or  not  one  goes  higher.  The  in- 
stance, and  the  direction  as  to  the  oil-bath  are  not  of  the  essence  of 
the  invention.  It  has  been  proved  that  the  temperature  and  the 
proportions  are  vital.  As  to  the  water-gas,  if  one  purifies  it,  one  does 
something  that  makes  the  hydrogen  operative,  and  so  the  process 
comes  within  Claim  1.  If  the  words  "  temperature  is  immaterial  " 
are  of  general  application  to  the  Specification,  they  are  misleading 
and  invalidate  the  Patent;  if  they  refer  only  to  the  specific  instance 
then  the  Specification  is  insufficient  as  to  the  general  process.  The 
differences  of  opinion  between  the  experts  have  been  narrowed  down 
to  the  mode  of  preparation  of  the  catalyst  —  the  nickel.  Mr.  Hehner 


316  APPENDIX 

used  temperatures  of  about  300°  for  the  reduction  of  the  oxide,  and 
sometimes  went  to  340°;  Dr.  Liebmann  went  as  high  as  360°  in  one 
case.  The  question  is  further  narrowed  down  to  the  preparation  of 
the  oxide.  The  process  can  be  carried  out  with  finely-divided  metal 
obtained  from  any  oxide,  but  only  with  certain  bodies,  and  with  cer- 
tain precautions.  Moissari's  Papers  have  no  bearing  on  the  matter. 
His  Paper  of  1880  was  simply  directed  to  the  investigation  of  the 
allotropy  of  certain  oxides.  The  experiments  of  the  Plaintiffs' 
witnesses  had,  in  order  to  succeed,  to  be  conducted  with  special 
stirring  apparatus  and  a  strong  current  of  hydrogen,  precautions  that 
are  not  indicated  by  the  Patentee.  The  failure  of  Dr.  Lewkowitsch 
to  obtain  Normann's  results,  although  following  his  Specification  care- 
fully, shows  that  the  Specification  is  insufficient.  The  Patentee 
assumed  that  the  catalyst  that  would  act  with  the  gases  would  act 
with  the  liquids,  and  it  turned  out  that  it  would  not.  As  to  infringe- 
ment, the  Defendants'  method  is  an  improvement  on  the  Patentee's, 
and  if  his  claim  is  limited  to  his  precise  description,  it  is  not  an  equiv- 
alent. 

Sir  A.  Cripps  K.C.  replied.  —  As  to  the  knowledge  at  the  date  of  the 
Patent,  the  references  to  Sabatier  imply  a  reference  to  Moissan,  and 
Sabatier  says  that  the  best  method  is  to  prepare  the  catalyst  in  the 
way  described  by  Moissan,  that  is,  in  order  to  get  a  porous  oxide, 
hydrate  should  be  used.  The  Plaintiffs'  witnesses  went  through  the 
sesquioxide  and  the  hydrate  to  the  protoxide,  and  showed  that  the 
process  worked  best  in  that  way.  They  tried  further  experiments 
with  oxides  made  from  the  carbonate,  sulphate,  and  nitrate,  and  suc- 
ceeded. The  invention  is  of  enormous  value;  it  is  said  to  be  worth 
a  quarter  of  a  million  a  year;  and  there  can  be  no  question  as  to  utility, 
or  as  to  the  sufficiency  of  the  statement  of  the  invention.  The  only 
question  is  as  to  the  sufficiency  of  the  directions.  The  stirrer  and  the 
strong  current  of  hydrogen  used  by  the  Plaintiffs'  witnesses  were 
expedients  such  as  would  naturally  be  adopted  by  a  chemist  wishing 
to  get  contact  between  the  reagents.  Supposing  the  invention  to 
be  the  hydrogenation  of  unsaturated  fatty  acids,  and  oils  so  as  to 
saturate  them,  and  the  Patentee  gives  one  example  that  works,  that 
is  sufficient.  Possible  complications  with  different  catalysts  have 
nothing  to  do  with  the  matter.  With  regard  to  the  presence  of  sul- 
phuretted hydrogen  in  water-gas  or  illuminating  gas,  a  chemist  would 
know  that  sulphur  is  a  "  poison  "  to  the  catalyst  and  would  remove 
it  from  the  water-gas,  and  it  is  not  found  in  modern  illuminating  gas. 
The  direction  that  the  catalyst  is  to  be  finely  divided  is  sufficient  to 
indicate  that  it  is  to  be  as  finely  divided  as  possible.  The  use  in  the 


APPENDIX  317 

Claim  of  the  expression  "  adapted  to  act  as  a  catalyst  "  has  been 
objected  to,  but  such  a  description  is  properly  employed  in  a  claim 
for  a  wide  principle.  The  further  experiments  of  Dr.  Liebmann  and 
Dr.  Passmore  were  conducted  in  accordance  with  the  directions  given 
in  the  Specification.  They  started  with  a  fine  nickel  powder  obtained 
by  reduction  in  a  current  of  hydrogen,  added  to  it  oleic  acid,  as  pure 
as  possible,  heated  it  over  an  oil  bath  and  passed  a  strong  current  of 
hydrogen  through  it,  so  as  to  keep  the  metal  in  a  state  of  suspension. 
They  succeeded,  and  the  only  objection  made  is  that  they  added 
stirring,  but  that  is  an  expedient  that  would  naturally  and  properly 
be  adopted. 

Neville  J.  —  The  Specification  in  the  present  case  is  short  and  in- 
artificial. The  Patentee  discloses,  I  think,  clearly  enough  what  he 
claims  to  have  discovered.  It  was,  in  the  first  instance,  that  the  satu- 
ration by  hydrogen  or  hydrogenation  of  unsaturated  fatty  acids  and 
their  glycerides,  fats  and  oils,  could  be  attained  by  catalysis.  In  in- 
troducing his  discovery,  he  refers  to  the  fact  that  it  had  already  been 
disclosed  that,  in  certain  cases,  catalytic  action  with  hydrogen  had 
been  brought  about  by  the  presence  of  finely-divided  platinum,  and 
further  that  Sabatier  and  Senderens  had  extended  discovery  in  this 
direction  by  showing  that  other  finely-divided  metals,  namely,  iron,  co- 
balt, copper,  and  especially  nickel,  might  take  the  place  of  platinum. 
He  tells  us  that  Sabatier  —  I  will  use  this  name  as  including  Senderens 
—  obtained  saturated  hydrocarbons  from  unsaturated  hydrocarbons 
(partly  with  simultaneous  condensation,  which  I  take  to  mean  what 
he  calls  later  secondary  reactions),  namely,  acetylene,  ethylene,  or 
benzene,  by  causing  their  vapours  mixed  with  hydrogen  gas  to  pass 
over  one  of  the  said  metals.  Reading  the  Specification  as  a  whole,  I 
think  he  then  proceeds  to  tell  us  that  his  discovery  is  that  it  is  easy  by 
"  this  catalytic  method  "  -  which  means,  I  think,  hydrogenation  by 
catalysis  —  to  hydrogenise  all  kinds  of  unsaturated  fatty  acids  and 
their  glycerides,  that  is  to  say,  fats  and  oils.  I  may  say,  in  passing, 
that  the  glyceride  is  merely  the  fatty  acid  with  the  addition  of  gly- 
cerine, and  the  fats  and  oils,  thus  composed,  differ  from  the  fatty  acids 
in  this  respect,  that  while  fatty  acids  may,  under  certain  conditions 
be  vaporised,  fats  and  oils  cannot.  How  to  vaporise  a  fatty  acid  the 
Specification  does  not  tell  us,  but  Normann  says  that  hydrogenation 
of  the  unsaturated  fatty  acid  may  be  obtained  by  causing  it  in  vapour 
with  hydrogen  to  pass  over  the  catalytic  metal.  This  vaporisation, 
however,  he  declares  to  be  unnecessary,  since  it  is  sufficient  to  expose 
the  fat  or  fatty  acid  —  that  is  to  say,  any  unsaturated  fatty  acid  or  its 
glyceride  —  in  a  liquid  condition  to  the  action  of  hydrogen  and  the 


318  APPENDIX 

catalytic  substance.  The  evidence  shows  the  advantage  of  treating 
the  fats  and  fatty  acids  in  the  liquid  state  without  vaporisation  to  be 
very  great,  and  I  think  Normann  did  not  intend  to  indicate  vaporisa- 
tion as  part  of  his  process,  but  to  point  out  that  you  could  obtain  hydro- 
genation  by  a  far  simpler  method.  To  dismiss  this  point  at  the  outset, 
I  do  not  think,  upon  any  construction  of  the  Specification,  that  the 
difficulty  of  vaporisation,  even  if  it  were  as  great  as  the  Defendants 
suggest,  would  avoid  the  Patent.  If  the  Specification  is  sufficient  in 
other  respects,  what  Normann  here  says  is  true,  and,  even  if  the  proc- 
ess by  vaporisation  is  of  no  commercial  value,  the  liquid  process  is, 
and  I  think  the  Patent  would  stand.  Having  told  us  that  treatment 
in  the  liquid  state  suffices,  Normann  discloses  an  instance  in  which  he 
alleges  that  pure  oleic  acid  may  be  completely  converted  into  stearic 
acid,  that  is,  a  non-saturated  fatty  acid  into  a  saturated  fatty  acid. 
I  think,  if  he  has  described  a  process  by  which  this  may  be  done,  and 
if  that  process  is  effective  with  all  fats  and  oils  and  all  other  fatty  acids 
in  combination  with  any  "  finely-divided  metal  adapted  to  act  as  a 
catalyser  "  (including  platinum,  iron,  cobalt,  copper,  and  nickel),  the 
Specification  would  be  sufficient.  Indeed,  I  should  be  inclined  to  hold 
that,  if  the  invention  was  substantially  co-extensive  with  the  Claim, 
proof  that  some  fatty  acid  or  oil  could  not  be  successfully  treated  by 
one  or  more  of  the  catalysers  mentioned  was  immaterial,  so  long  as  the 
exception  was  of  no  commercial  importance. 

There  are  minor  points  upon  the  construction  of  the  Specification 
raised,  such  as  the  possibility  of  using  commercial  gas  mixtures  as  a 
substitute  for  hydrogen,  but  I  will,  in  the  first  instance,  examine  the 
question  of  whether  the  process  which  Normann  describes  will  effect 
the  result  which  he  claims  for  it,  and  I  will  here  say  that,  if  by  his  proc- 
ess a  substantial  saturation  is  effected,  sufficient  for  technical  pur- 
poses, I  should  not  consider  its  failure  to  ensure  complete  saturation 
fatal,  notwithstanding  that  he  has  stated  that  the  oleic  acid  may  be 
completely  converted  into  stearic  acid;  nor  should  I  think  it  fatal  if 
some  secondary  reaction  took  place,  notwithstanding  his  declaration 
to  the  contrary,  so  long  as  such  reactions  did  not  substantially  interfere 
with  the  utility  of  the  process. 

In  my  judgment,  the  right  of  a  Patentee  to  his  monopoly  is  essen- 
tially a  matter  of  substance,  and  the  question  to  be  decided  a  broad 
one,  namely,  whether  he  has  in  substance  given  the  consideration 
which  the  grant  of  the  Patent  requires. 

Now  let  us  turn  to  Normann's  Specification  and  see  what  are  the 
conditions  to  be  fulfilled  to  obtain  the  result  which  he  indicates.  First 
of  all,  nickel  powder  obtained  by  reduction  in  a  current  of  hydrogen  is 


APPENDIX  319 

to  be  procured.  There  is  no  special  meaning,  I  think,  to  be  attached 
to  the  word  "  powder,"  except  that  the  product  is  to  be  in  a  fine  state 
of  division;  but  the  evidence  shows  that,  if  metallic  nickel  is  to  be 
obtained  by  reduction,  it  must  be  obtained  by  reduction  of  the  oxide; 
so  we  take  finely-divided  nickel  obtained  by  reduction  of  nickel  oxide 
in  hydrogen  and  add  it  to  chemically  pure  oleic  acid.  For  pure  oleic 
acid,  we  may  substitute  any  commercial  fatty  acid,  or  fat,  so  far  as  the 
method  is  concerned;  though,  of  course,  if  we  do,  we  cannot  expect 
complete  conversion  of  the  whole  compound,  inasmuch  as  impurities 
may  be  expected.  Then  the  oleic  acid  is  to  be  heated  over  an  oil-bath. 
No  temperature  is  mentioned.  The  ordinary  temperatures  for  which 
oil-baths  are  used  are  variously  stated  as  extending  from  50°  or  100°  to 
250°  C.,  but,  inasmuch  as  the  inventor  tells  us  immediately  after  that 
the  quantity  of  nickel  added  and  the  temperature  are  immaterial  and 
will  only  affect  the  duration  of  the  process,  I  think  it  is  impossible  to 
construe  the  Specification  as  giving  any  direction  as  to  the  temperature 
to  be  employed,  unless,  perhaps,  one  may  say  that,  as  heating  is 
directed,  it  should  be  something  above  room  temperature  —  how  much, 
I  think,  one  does  not  learn.  A  strong  current  of  hydrogen  is  to  be 
passed  through  the  mixture,  and  I  think  it  is  common  ground  that  the 
current  should  be  strong  enough  to  keep  the  metallic  nickel  suspended 
in  the  liquid  in  order  to  give  the  opportunity  of  contact  between  the 
surface  of  the  nickel  and  the  molecules  of  the  other  bodies. 

Before  proceeding  further,  I  will  put  in  untechnical  language  what 
I  understand  from  the  evidence  to  be  conveyed  by  the  word  "  catal- 
ysis." It  appears  that  in  the  presence  of,  or  in  contact  with,  certain 
metals,  chemical  bodies  undergo  changes  which  do  not  otherwise  take 
place.  The  reactions  induced  by  the  presence  of  the  catalyst  may 
involve  merely  the  splitting  up  of  a  single  chemical  body,  of  which  the 
decomposition  of  acetylene  in  the  presence  of  finely-divided  nickel  is 
an  instance,  or  the  combination  of  two  chemical  bodies  which,  but 
for  contact  with  the  catalyst,  would  have  retained  their  composition 
unchanged,  although  in  contact  with  one  another.  The  hydrogena- 
tion  of  a  fatty  acid  where  hydrogen  and  the  fatty  acid  are  brought 
into  contact  in  the  presence  of  a  suitable  catalyst  is  an  instance  of  the 
latter  kind  of  reactions,  and  that  which  forms  the  subject-matter 
of  the  present  invention. 

To  return  to  the  Specification,  the  experiments  made  by  Mr. 
Ballantyne  and  Mr.  Hehner  show  that  you  may  take  finely-divided 
nickel,  or  nickel  powder,  obtained  by  reduction  from  the  oxide  in  a 
current  of  hydrogen,  and  add  it  to  pure  oleic  acid  or  any  other  fatty 
acid,  warm  the  mixture,  and  pass  through  it  a  strong  current  of  hydro- 


320  APPENDIX 

gen,  without  obtaining  the  catalytic  reaction  indicated  by  the  Paten- 
tee at  all.  That,  by  preparing  your  nickel  powder  in  a  special  way 
and  raising  the  temperature  to  a  certain  degree,  you  may  obtain  the 
result  required,  although  the  reaction  appears  to  be  very  capricious, 
is  shown  by  the  experiments  of  Dr.  Liebmann  and  Dr.  Passmore  and 
admitted  by  Mr.  Ballantyne.  The  Plaintiffs'  contention  is  that  the 
success  of  Dr.  Liebmann  and  Dr.  Passmore  is  conclusive  to  establish 
the  validity  of  the  Patent,  for  it  is  said  that  these  gentlemen  did  no 
more  than  the  Specification  directed.  They  say  that  it  was  known 
in  1903  that  catalysis  was  a  surface  or  contact  action,  and  that,  for 
the  purpose  of  obtaining  contact,  the  finer  the  division  the  better  the 
chance,  and  that  it  was  known  that,  for  the  purpose  of  catalysis,  the 
oxide  should  be  reduced  to  the  metal  at  the  lowest  possible  temper- 
ature, or  at  about  300°  C.  Therefore,  they  say  that  any  competent 
chemist  upon  reading  the  Specification  would,  as  of  course,  take 
nickel  oxide  as  finely-divided  as  possible,  and  reduce  it  in  hydrogen 
at  a  temperature  of  from  300°  to  350°. 

I  pause  here  to  state  certain  conclusions  at  which  I  have  arrived 
upon  the  evidence.  It  appears  that  the  fineness  of  division  of  the 
nickel  —  by  which  is  meant  the  minuteness  of  the  pieces  composing 
the  substance,  depends  —  not  upon  the  temperature  (within  the 
ranges  of  temperature  which  are  dealt  with  here)  at  which  the  oxide  is 
reduced  to  the  metal,  but  upon  the  physical  state  of  the  oxide  with 
regard  to  minuteness  of  division  at  the  time  when  the  reduction  com- 
mences, the  number  of  pieces  of  metal  after  the  reduction  being  sub- 
stantially the  same  as  the  number  of  pieces  in  the  oxide.  Therefore, 
the  temperature  at  which  the  reduction  takes  place  is  in  this  connec- 
tion immaterial.  The  activity  of  a  catalyst  does  not,  however,  I 
think,  depend  solely  upon  minuteness  of  division,  but  upon  the  po- 
rosity of  the  pieces  of  metal  composing  the  powder.  In  the  course  of 
reduction,  when  the  oxide  gives  up  its  oxygen,  the  metal  left  behind 
is  in  a  porous,  or  what  has  been  described  as  a  cavernous  condition, 
the  result  being  that,  inasmuch  as  the  fatty  substance  may  be  able 
to  penetrate  into  the  cavities,  a  greater  surface  is  afforded  for  contact 
than  if  it  were  in  a  denser  or  more  solid  condition.  This  distinction 
has,  I  think,  not  been  sufficiently  regarded  in  some  parts  of  the 
evidence,  the  words  "  finely-divided  "  having  been  sometimes  used 
to  denote  porosity,  rather  than  the  smallness  of  the  pieces  into  which 
the  metal  is  divided.  Mr.  Ballantyne,  explaining  the  different  quali- 
ties required  for  pyrophoric  purposes  and  catalytic  purposes,  speaks  of 
metal  in  larger  particles  or  grains  being  more  finely-divided  than  metal 
in  smaller  particles  or  grains.  I  do  not  think  that,  in  fact,  the  words 


APPENDIX  321 

"  finely-divided  "  have  a  meaning  in  chemistry  different  from  that 
which  they  bear  in  English.  The  effect  of  heating  is  to  cause  the 
porous  metal  to  contract  and  become  denser;  hence  the  desirability 
of  reducing  the  oxide  at  a  low  temperature;  and  I  think  to-day  it 
would  be  common  ground  that  the  most  promising  catalyst  for  hydro- 
genation  would  be  a  suitable  metal  in  the  highest  state  both  of  fine 
division  and  porosity.  At  the  same  time,  it  must  be  remembered  that 
this  so-called  catalysis  remains  unexplained.  All  that  is  known 
about  it  is,  that  it  happens,  and  no  one  can  safely  predict  what  will 
happen  in  any  case  not  already  tested  by  experiment.  Nothing 
seemed  more  unlikely  before  Normann's  discovery  than  that  this  cata- 
lytic method  should  be  available  for  the  saturation  of  fats  and  oils. 

Papers  by  Moissan  and  Sabatier  are  relied  upon  by  the  Plaintiffs 
in  two  ways:  first,  because  Sabatier  is  referred  to  in  the  Specification, 
and  Moissan  is  referred  to  by  Sabatier,  and  it  is  said  that  this  is  an 
express  reference  by  the  Patentee  adding  to  the  information  given 
by  the  Specification  all  the  information  to  be  gleaned  from  these 
Papers,  and  in  them,  it  is  said,  are  to  be  found  directions  how  to  pre- 
pare your  catalysts  for  Normann's  invention;  and,  secondly,  it  is 
said  that,  at  all  events,  what  was  contained  in  them  was  public  knowl- 
edge, and  the  hypothetical  competent  chemist  was  bound  to  supple- 
ment the  Specification  with  the  knowledge  acquired  from  Sabatier. 

The  first  contention  is,  in  my  judgment,  untenable.  It  may  per- 
haps be  permissible  for  a  Patentee  to  say  in  his  Specification:  —  "  For 
"  the  purpose  of  carrying  my  invention  into  effect,  I  refer  you  to  such 
"and  such  a  publication  in  which  you  will  find  all  necessary  directions." 
I  doubt  if  this  would  fulfil  his  obligations  to  the  public,  but,  at  all 
events,  on  turning  to  the  publication  indicated,  you  must  find  in  clear 
and  precise  terms  the  very  process  which  he  claims,  or  one  which, 
without  further  experiment,  can  be  applied  for  the  carrying  into  effect 
of  his  invention.  To  turn  the  hypothetical  chemist  loose  into  the 
labyrinth  of  long  chemical  papers  dealing  with  a  variety  of  subjects 
more  or  less  connected  with  the  matter  in  hand,  and  tell  him  to  search 
for  himself  and  adopt  for  the  purposes  of  the  invention  what  he 
deems  applicable,  would  be  to  fall  altogether  short  of  his  duty  as 
patentee.  On  the  question  of  common  knowledge,  I  think  there 
must  be  shown  something  more  than  the  fact  that  there  has  been 
recently  published  information  which,  though  not  directed  to  the 
matter  in  hand,  ought,  if  properly  understood  and  digested,  to  have 
led  the  inquirer  to  adopt  certain  methods  and  precautions  in  carry- 
ing out  the  invention  with  regard  to  which  the  Specification  is  silent. 
But  further,  if  every  line  of  Moissan  and  Sabatier  were  read,  I  do  not 


322  APPENDIX 

think  it  would  lead  the  inquirer  to  suppose  that  any  particular 
method  of  preparing  the  oxide  for  the  purposes  of  Normanris  process 
was  necessary,  nor  indeed,  as  the  experiments  show,  was  it.  Mois- 
san's  Paper  is  a  description  of  an  isolated  demonstration  of  the  reduc- 
tion of  a  sesquioxide  of  nickel  prepared  in  a  particular  way  through 
various  transformations  down  to  metallic  nickel,  and  is  referred  to  by 
Sabatier  in  a  Paper  but  remotely  bearing  upon  Normanri's  invention. 
It  is  true  that  Moissan  declares  that  the  resulting  metallic  nickel  will 
be  pyrophoric,  but  it  appears  to  me  that  there  is  no  direct  connection 
between  a  metal  being  pyrophoric  (that  is,  being  in  a  state  in  which 
it  will  oxidise  in  ordinary  temperature  at  a  white  heat)  and  being  a 
catalyst  which  can  be  relied  upon  to  realise  successfully  Normanris 
invention.  Indeed,  the  fact  that  some  of  the  catalysts  used  by  Mr. 
Ballantyne  and  Mr.  Hehner  in  unsuccessful  experiments  were  pyro- 
phoric, seems  conclusive  on  this  point.  1  think,  therefore,  the  question 
of  how  to  prepare  a  finely-divided  metal  so  that  it  may  be  pyrophoric 
is  not  relevant  to  the  present  case. 

I  come  to  the  conclusion,  upon  the  evidence,  that  Normanris 
process  will  not  produce  the  result  he  claims  for  it  unless  the  fine  nickel 
powder  is  obtained  in  a  special  manner  not  indicated  by  the  Specifica- 
tion, or  unless  a  very  strong  current  of  hydrogen  is  used,  and  mechan- 
ical stirring  or  some  other  special  device  is  resorted  to.  The  possible 
effect  of  violent  agitation  in  keeping  the  surface  of  the  catalyst  free 
from  the  poison  of  the  oil  is  pointed  out  by  Mr.  Ballantyne.  No  hint 
of  such  a  necessity  is  to  be  found  in  the  Specification,  and  I  think  the 
hypothetical  chemist  was  entitled  to  suppose  that  the  process  de- 
scribed in  the  Specification  was  sufficient  to  effect  its  purpose,  and, 
having  applied  that  process  and  failed  to  produce  the  result,  was 
entitled  to  consider  himself  misinformed,  without  resorting  to  exper- 
iment to  see  in  what  manner  the  directions  failed.  The  discovery 
was  entirely  new  and  contrary  to  anticipation,  and  the  process  de- 
scribed by  Normann,  for  all  that  was  generally  known  on  the  subject, 
might  very  well  have  been  sufficient.  There  was  no  reason  to  pre- 
sume any  necessity  to  add  to  the  directions,  which  he  gave,  anything 
from  the  stock  of  common  knowledge.  What  appears  to  me  very 
strong  confirmation  of  the  insufficiency  of  the  Specification  is  to  be 
found  in  the  evidence  of  Dr.  Lewkowitsch,  a  great  authority  on  the 
subject.  Dr.  Lewkowitsch  had  endeavoured  himself  to  obtain  the 
saturation  of  oleic  acid  by  the  use  of  nickel  as  a  catalyst  and  had 
failed.  He  afterwards  became  acquainted  with  Normann' s  Specifica- 
tion, and  tried  a  further  series  of  experiments  with  no  greater  success. 
He  had  obtained  his  catalyst  from  a  solution  of  sulphate  of  nickel. 


APPENDIX  323 

He  afterwards  read  some  further  Papers  by  Sabatier,  published  in 
1905,  recommending  amongst  other  things  the  use  of  nitrate  in  place 
of  sulphate  of  nickel,  and  pointing  out  that  nickel  lost  its  catalytic 
properties  if  exposed  to  too  high  a  temperature.  With  these  hints, 
Dr.  Lewkowitsch  recommenced  his  experiments,  and  after  several 
years  succeeded  in  solving  the  problem.  It  is  said  for  the  Plaintiffs, 
and  truly  said,  that  sulphur  was  known  to  be  what  is  called  a  poison 
to  a  catalyst  and  that  therefore  sulphate  of  nickel  ought  not  to  have 
been  employed,  but  the  precipitate  was  properly  washed,  and  there 
was,  in  1903,  no  reason  to  suppose,  if  this  was  done,  that  sulphur 
to  an  injurious  extent  would  remain.  Moreover,  no  warning  is  given 
in  Normann's  Specification  against  the  use  of  sulphate  of  nickel,  or 
as  to  the  temperature  to  be  employed  in  reduction.  The  evidence 
in  this  case  shows  that  a  catalyst  prepared  from  the  sulphate  may 
be  successful,  and  also  that  nickel  may  be  heated  to  a  red  heat  with- 
out destroying  its  catalytic  properties.  Certain  passages  in  subse- 
quent publications  of  Dr.  Lewkowitsch  have  been  referred  to  as  dis- 
counting the  evidence  given  by  him  in  this  action.  It  seems  to  me 
that  they  do  not  diminish  the  weight  of  his  testimony.  Here  was  a 
chemist,  having  special  acquaintance  with  the  subject,  who  tried  a 
method  of  saturating  oleic  acid,  identical  with  that  described  by  Nor- 
mann,  and  failed,  studied  Normann's  Specification  and,  after  repeated 
experiments,  again  failed,  and,  after  receiving  what  he  says  was  a 
clue  from  a  publication  by  Sabatier  in  1905,  succeeds  only  then  after 
experiments  extending  over  several  years.  So  that  we  find  a  chemist 
of  exceptional  qualifications,  deeply  interested  in  the  subject,  failing 
for  years,  after  repeated  experiments,  and  careful  study  of  Normann's 
Specification,  to  achieve  what  I  am  asked  to  believe  any  competent 
chemist  could,  in  1903,  have  achieved  by  following  Normann's  direc- 
tions, without  any  experiment  at  all. 

In  this  connection  I  cannot  but  remind  myself  that,  though  the 
Patent  was  taken  out  in  1903  and  purported  to  reveal  a  process  of 
immense  commercial  value,  no  evidence  has  been  called  to  show  that 
anyone  succeeded  in  taking  advantage  of  the  discovery  for  a  consider- 
able number  of  years  after  its  publication;  that  the  only  evidence  of 
sufficiency  is  the  evidence  of  eminent  chemists  who  essay  to  prove  by 
experiments  in  1912  that  the  directions  contained  in  the  Specification 
were  in  1903  sufficient  to  ensure  success. 

I  come  to  the  conclusion  that  the  directions  in  Normann's  Specifi- 
cation were  insufficient;  and  I  infer,  both  from  the  evidence  before  me, 
and  the  lack  of  evidence,  that,  great  as  the  discovery  that  unsaturated 
fatty  acids  and  their  glycerides  could  be  hydrogenated  by  the  catalytic 


324  APPENDIX 

method  undoubtedly  was,  no  practical  means  of  taking  advantage  of 
the  discovery  were  disclosed  until  after  further  experiment  subsequent 
to  the  date  of  the  Patent. 

It  has  been  repeatedly  urged  that,  catalysis  depending  upon  contact, 
the  difference  between  success  or  failure  is  simply  a  question  of  obtain- 
ing or  failing  to  obtain  contact.  In  my  opinion,  the  evidence  fails  to 
establish  this  in  any  material  sense.  There  is  nothing  to  show  that 
the  directions  of  Normann  do  not  suffice  to  get  contact.  Catalysis 
remains  a  mystery  to-day,  and  in  1903  nothing  whatever  was  known 
as  to  the  means  necessary  to  obtain  successful  contact  in  the  catalytic 
hydrogenation  of  oleic  acid,  or  any  other  fatty  acid  or  glyceride,  except 
what  was  disclosed  by  Normann  himself.  According  to  Mr.  Ballan- 
tyne's-  evidence,  a  catalyst  which  succeeded  in  getting  "  contact  "  in 
this  sense  with  acetylene  after  Sabatier,  failed  with  Normann' 's  process. 
To  say  that  a  direction  to  pass  a  strong  current  of  hydrogen  through  a 
mixture  of  fine  nickel  powder  and  oleic  acid,  in  order  to  expose  the  acid 
to  the  action  of  hydrogen  and  the  catalytic  substance,  connotes  the 
resort  to  every  device  known  to  science  for  making  the  exposure  as 
complete  or  as  frequent  as  possible,  seems  to  me  extravagant. 

I  therefore  come  to  a  conclusion  adverse  to  the  Plaintiffs'  contention 
upon  their  own  case;  but  I  do  not  concur  in  the  construction  of  the 
Specification  put  forward  on  their  behalf.  It  has  been  contended  that 
this  is  a  Patent  for  a  principle,  and  that  if  the  Patentee  shows  one  way 
of  carrying  it  out  he  is  entitled  to  claim  for  all  ways.  If  Normann  had 
invented  the  hydrogenation  of  oleic  acid  by  help  of  a  nickel  catalyst, 
and  had  given  sufficient  information  in  the  instance  stated  to  ensure 
success,  then  I  think  he  could  rightly  claim  all  other  ways  of  arriving 
at  the  result ;  but  here  he  claims  to  have  invented  a  method  of  obtain- 
ing hydrogenation  of  all  unsaturated  fatty  acids  and  their  glycerines, 
and  if  his  method  fails  in  any  one  case  I  think  his  Patent  would  be  bad. 
Moreover,  he  claims  to  be  able  to  secure  the  result  by  the  use  of  finely- 
divided  platinum,  iron,  cobalt  and  copper  as  well  as  nickel,  and  if  the 
use  of  any  one  of  these  catalysts  is  fatal  to  his  process  I  think  his  Patent 
is  bad. 

There  are  other  matters  arising  in  the  action  which,  having  regard 
to  the  view  already  expressed,  are  not  necessary  for  the  decision  of  the 
case;  bub  1  may  say  that  I  think  that  the  evidence  shows  that  the 
temperature  at  which  hydrogenation  is  attempted  is  material,  not  only 
with  regard  to  time  occupied  in  obtaining  the  desired  reaction,  but  for 
obtaining  such  reaction  at  all.  It  may  be  that  one  element  of  success 
is  the  mixture  of  oxide  of  nickel  with  the  metal.  Dr.  Liebmann's 
experiments,  were  with  reduction  at  a  low  temperature,  300°  to  320° 


APPENDIX  325 

for  a  short  period,  one  hour,  while  Mr.  Hehner  in  the  experiments 
referred  to  reduced  at  360°  for  three  hours.  I  think  the  evidence 
shows  that  the  temperature  and  time  employed  by  Dr.  Liebmann  can- 
not be  relied  upon  to  obtain  complete  reduction.  It  will  be  observed 
that  both  Dr.  Liebmann  and  Dr.  Passmore,wheu  seeking  to  demonstrate 
that  catalysts  prepared  in  a  manner  similar  to  that  adopted  by  the 
Defendants'  witnesses  could  be  used,  not  only  in  all  cases  resorted  to 
stirring,  but  used  a  much  larger  current  of  hydrogen  than  that  used 
in  previous  experiments.  Having  heard  the  evidence  upon  the  point, 
I  will  add  that,  could  Normann's  Patent  have  stood,  in  my  judgment, 
the  Defendants  would  have  infringed  it. 

In  the  result,  I  am  of  opinion  that  the  Plaintiffs'  action  fails  and 
must  be  dismissed  with  costs. 


INDEX 


Abel,  50. 

Abelous,  104. 

Aboulenc,  56. 

Absorption,  118. 

Acetate  nickel,  68,  80. 

Acetates  of  metals,  47,  72. 

Acetylene,  54,  217. 

Acetyl  number  of  castor  oil,  126. 

Acids,  action  on  spent  catalyzer,  75. 

Acidity  of  hardened  oil,  158. 

Acid,  oleic,  70,  195. 

Acid,  use  of,  to  remove  catalyzer,  71. 

Acids,  fatty,  98. 

Action  of  catalyzers,  310,  311. 

Adams,  188. 

Addition  of  hydrogen,  111. 

Adsorption,  118. 

Agitation  of  catalyzer  in  oil,  26. 

Agitation  with  screen-covered  paddles, 
15. 

Agulhon,  50. 

Aigner,  279. 

Albumin,  51. 

Altmayer,  117. 

Aluminum,  61. 

Amberger,  6,  108,  109. 

American  Linseed  Co.,  188. 

American  Oxhydric  Co.,  268. 

Amorphous  carbon,  120. 

Amorphous  palladium,  118. 

Analytical  constants,  123. 

Andrew,  115. 

Aniline,  5,  7. 

Animal  fats,  98. 

Anticatalytic  bodies,  104. 

Apparatus  for  hydrogenation,  192. 

Apparatus  for  reducing  catalytic  mate- 
rial, 76. 

Apparatus  of  Wilbuschewitsch,  46. 

Arachidic  acid,  127,  128. 

Atack,  138. 

Auerbach,  145. 


Aufrecht,  136. 

Autoclave  saponification,  172. 

Badische  Co.,   110,  205,  207,  222,  239, 

256,  298. 
Ballantyne,  319. 
Bamberger,  247. 
Bartels,  70. 
Barth,  280. 
Barton,  243. 
Barus,  199. 

Basic  soaps  of  heavy  metals,  71. 
Baskerville,  82. 

Baskets  containing  catalyzer,  22. 
Baudouin  test,  98,  127. 
Becchi  test,  98,  127. 
Bedford,  8,  12,  13,  19,  50,  51,  60,  63,  64, 

65,  70,  72,  75,  80,  213. 
Behenic  acid,  127,  196. 
Belou,  240. 
Benker,  277. 
Bennie,  246. 
Bergius,  254,  255. 
Bergo,  172,  187. 
Berlin  Anhaltische  Maschinenbau  A-G., 

240. 

Berthelot,  89. 
Bianchi,  136. 
Birkeland,  36. 
Blown  oils,  124. 
Blum,  196. 
Boberg,  62,  84. 
Bock,  49,  247. 
Bodies,  anticatalytic,  104. 
Bohm,  67,  149,  183. 
Bohringer,  C.  F.,  and  Sohne,  5. 
Bomer,  125,  131,  145,  146. 
Borneol,  70. 
Boron,  85. 
Boron  hydride,  85. 
Bosch,  2,  19. 
Bouant,  146. 


327 


328 


INDEX 


Boudouard,  206. 
Boyce  process,  155. 
Boynton,  293. 
Bragnier,  3. 
Brahmer,  197. 
Bramkamp,  294. 
Brebesol,  144. 
Bredig,  33,  101. 
.Bremen  Besigheimer  Olfabriken,  7,  43, 

74,  81,  144. 
Breteau,  79. 
Brindley,  246. 
Brochet,  36. 

Brunner,  Mond  &  Co.,  307. 
Bruno,  245. 
Bruno  Waser,  5. 
Buffa,  282. 
Bulteel,  20. 
Burdett,  257,  283. 
Bureau  of  Animal  Industry,  147. 
Butter    substitute,    hydrogenated,    153, 

154. 
Buttlar,  32. 

Calvert  system,  44. 

Camphor,  70. 

Candelite,  125,  126,  129,   163,  169,  174, 

175,  176,  187. 
Candle  material,  179,  182. 
Carbon  dioxide  treatment  of  catalyzer, 

79. 
Carbon  dioxide,   treatment  of  reduced 

nickel  with,  74. 

Carbon  monoxide,  action  on  lime,  202. 
Carbon  monoxide  as  a  catalyzer  poison, 

106. 

Carbon  monoxide,  effect  of,  in  fat  hard- 
ening, 40. 
Carbon  monoxide,   effect  on  catalyzer, 

198. 

Carbon  monoxide,  effect  on  nickel,  199. 
Carbonium  Co.,  218. 
Carbonyl,  nickel,  20,  40,  41,  43,  69,  88. 
Caro,  40,  199,  210,  241. 
Carpenter,  299. 

Carrier,  metal  impregnated,  16. 
Carughi,  6. 
Castor  oil,  39,  98,  101,  104,   106,  121, 

125,  126,  139,  158,  160.      . 
Castor  oil,  hardened,  29. 


Catalytic  action  favored  by  formic  acid, 

82. 
Catalytic  metal  welded  to  metal  support, 

77. 
Catalyzer,     according     to     Wilbusche- 

witsch,  75. 

Catalyzer,  action  of  oil  on,  26. 
Catalyzer,  activity  of,  320. 
Catalyzer,  agitation  of,  in  oil,  26. 
Catalyzer,  boron,  85. 
Catalyzer,  collecting  in  an  atmosphere 

of  hydrogen,  85. 

Catalyzer,  collecting  in  water,  85. 
Catalyzer  containing  a  drying  agent,  82. 
Catalyzer,  "colloidal"  nickel  oxide,  64. 
Catalyzer,  copper,  51. 
Catalyzer,  definition  of,  50. 
Catalyzer,  diffusion  of  oil  to  and  from, 

26. 

Catalyzer,  drying  of,  81. 
Catalyzer,  easily  suspended,  81. 
Catalyzer,  effect  of  liquids  on,  55. 
Catalyzer,  from  nickel  carbonyl,  96. 
Catalyzer,  heavy  metal  soaps  for  making, 

40. 

Catalyzer,  iridium  as  a,  106. 
Catalyzer,  Kayser,  73. 
Catalyzer,  life  of,  55. 
Catalyzer,  nickel,  50,  51. 
Catalyzer,  nickel,  affected  by  liquids,  13. 
Catalyzer,  nickel  by  electric  current,  84. 
Catalyzer,  nickel  carbonyl  used  for,  20. 
Catalyzer,  nickel-cobalt,  70. 
Catalyzer,  nickel,  effect  of  alkali  on,  70. 
Catalyzer,  nickelized  pumice,  52 
Catalyzer   of   Techno-Chemical   Labor- 
atories Ltd.,  77. 

Catalyzer,  nickel  on  pumice,  27. 
Catalyzer,  nickel  oxide,  60,  84. 
Catalyzer,  osmium  as  a,  105,  106. 
Catalyzer,  palladium,  7,  21. 
Catalyzer  permanent  on  exposure,  74. 
Catalyzer  poisons,  14,  55,  199,  305. 
Catalyzer  poison,  sulfur  as,  54. 
Catalyzer,  porous,  320. 
Catalyzer,  preparation  of,  62. 
Catalyzer  protected  by  oil,  52. 
Catalyzer,  recovery  of,  74,  83. 
Catalyzer,  reduction  of,  87. 
Catalyzer,  reduction  temperature  for,  51. 


INDEX 


329 


Catalyzer,  rhodium  as  a,  106. 

Catalyzer,  ruthenium,  as  a,  106. 

Catalyzer,  treatment  for  preservation, 
63. 

Catalyzers,  50. 

Catalyzers,  action  of,  310,  311. 

Catalyzers,  classification  of,  59. 

Catalyzers,  colloidal  platinum  and  pal- 
ladium, 101,  102. 

Catalyzers,  continuous  reduction  of,  86. 

Catalyzers,  most  sensitive,  51. 

Catalyzers,  non-pyrophoric,  122. 

Catalyzers,  organic  salts  of  metals  used 
to  prepare,  47,  48. 

Catalyzers,  palladium,  105. 

Catalyzers,  platinum,  105. 

Catalyzers,  pyrophoric  qualities,  52. 

Catalyzers,  temperature  for  reducing,  57. 

Catalyzers,  treatment  in  vacuo,  81. 

Cathodic  reduction,  121. 

Centrifugal  apparatus  for  hydrogenating 
oils,  21. 

Cerium,  61,  110. 

Cerium  as  a  catalyzer,  21. 

Chandler,  104. 

Changes  taking  place  in  hardened  oils  on 
keeping,  147. 

Changes  taking  place  in  lard  compound, 
156. 

Charcoal,  120. 

Charcoal  and  nickel,  78. 

Chemical  considerations  in  fat  harden- 
ing, 41. 

Chemically  active  rays,  in  fat  hardening, 
41. 

Chem.  Fabr.  auf  Actien,  70. 

Chem.  Fabr.  Griesheim-Elektron,  200, 
201,  252. 

Chem.  Fab.  vorm.  Goldenberg,  108. 

Chilling  lard  compound,  140. 

Chinese  wood  oil,  162. 

Chlorine  a  catalyzer  poison,  51. 

Chocolate,  156. 

Cholesterol,  125,  126,  133,  136. 

Chrysalis  oil,  162. 

Circulation  of  hydrogen  through  oil,  25. 

Classification  of  catalyzers,  59. 

Claude,  209,  214,  215. 

Clausmann,  242. 

Claver,  241. 


Clay  support  for  catalyzer,  73. 

Clupanodonic  acid,  130,  196. 

Cobalt,  39,  121. 

Cobalt  catalyzer  on  metal  support,  78. 

Cobalt  formate,  72. 

Cobalt  hydride,  121. 

Cobalt-nickel  catalyzer,  70. 

Cobalt  oxide,  54,  64. 

Cobalt  reduced,  113. 

Cocoanut  charcoal,  120.  .       j       J 

Cocoanutoil,  124,  132, 133,  136, 140, 152, 

154,  156,  195. 
Cocoanut  oil  soaps,  168. 
Cod-liver  oil,  121. 

Codex  alimentarius  austriacus,  136. 
Coefficient  of  reduction,  68. 
Coke  oven  gas,  198. 
Collins,  271. 
Colloid,  protective,  103. 
Colloidal  osmium  dioxide,  105. 
Colloidal  palladium,  98,  102. 
Colloidal  platinum,  33,  101. 
Colloidal  platinum,   apparatus  for  use 

with,  105. 
Colophony,  139. 

Color  changes  in  lard  compound,  156. 
Color  reactions  of  hydrogenated  oils,  134. 
Common  expedients  involved  in  hydro- 

genation  processes,  67. 
Connstein,  29. 
Conroy,  50. 

Consortium  fur.  Elektro-chem.  Ind.,  250. 
Continuous  reduction  of  catalyzer,  86. 
Converting  surfaces,  11. 
Copper,  39. 

Copper  catalyzer,  50,  51,  54,  121. 
Copper  formate,  72. 
Copper  oxide  used  as  a  carrier,  77. 
Copper  soap,  71. 
Corn  oil,  124,  156,  195. 
Coryphol,  129. 
Cost  of  lard  compound,  144. 
Cottonseed  oil,  20,  39,  41,  48,  65,  72,  76, 

79,  82,  80,  85,  104,  123,  124,  125,  132, 

133,  140,  152,  305. 
Cottonseed  oil,  deodorization  of,  26. 
Cottonseed  oil,  Egyptian,  79. 
Cottonseed  oil,  hardening    with    nickel 

from  nickel  carbonyl,  97. 
Cottonseed  oil,  nickel  in,  149. 


330 


INDEX 


Cottonseed    oil,   treatment  with  nickel 

carbonyl,  20. 
Cowper-Coles,  279. 
Cripps,  307. 
Crisco,  16. 
Crisca,  136.       - 
Crosfield  &  Sons,  73,  76,  303. 
Crutolin,  169,  175,  184. 
Curve  showing  rate  of  hydrogenation,  70. 

Dansette,  279. 

D'Arsonval,  259. 

Davy,  292. 

Day,  10,  11,  20. 

Definition  of  catalyzer,  50. 

De  Hemptinne,  3,  30. 

Dehydrogenation,  113. 

de  Kadt,  37,  40,  71. 

de  Kadt  apparatus,  38. 

Dellwik-Fleischer  Wassergas-Ges.,  226. 

de  Montlaur,  107. 

De  Nordiske  Fabriker  De-No-Fa  Aktiesl- 

skap,  71,  161. 
Deodorization  of  oil,  26. 
Desulfurizing  petroleum,  11. 
Detection  of  hydrogenated  fats,  130. 
Deveaux,  154. 
Devices,  safety,  292. 
Devik,  36. 
Dewar,  96,  116. 
De  Wilde,  103,  304. 
Dibdin,  21. 

Dieffenbach,  203,  205,  239. 
Differential  heating,  22. 
Dimethylglyoxime,  130,  136,  137. 
Di  Nola,  136. 
Dioleostearin,  144. 
Distearopalmitin,  144. 
Distillation  under  diminished  pressure, 

14. 

Dobereiner,  107. 
Dry  hydrogen  in  reducing  operations, 

69. 

Dubovitz,  133,  181. 
Dubbs,  11. 

Eastwick,  244. 

Edgar,  114. 

Edibility  of  hydrogenated  oils,  144. 

Edible  hydrogenated  oils,  140. 


Edible  properties  of  hardened  whale  oil, 

149. 

Edible  qualities  of  hardened  oils,  147. 
Edison,  83. 

Effect  of  liquids  on  nickel  catalyzer,  13. 
Efrem,  108. 

Egyptian  cottonseed  oil,  79. 
Elaidic  acid,  29. 

Electric  current,  application  of,  32. 
Electric  current,  disintegrating  nickel  by, 

84. 

Electric  discharge,  44. 
Electric  discharge  process,  3,  31. 
Eiectrical  reduction  processes,  3. 
Electrolysis  of  brine,  196. 
Electrolytic  hydrogenation,  3. 
Eldred,  77,  204. 
Ellenberger,  202. 
Ellis,  1,  22,  25,  26,  32,  43,  48,  78,  84,  86, 

87,  97,  125,  152,  156,  157,  204,  291. 
Elsworthy,  215 
Elworthy,  52,  204,  206,  231. 
"Emulsion"  of  oil  and  catalyst,  72. 
"Emulsion"  of  oil  and  catalyzer,  75. 
Enclosed  motor  hydrogenator,  45. 
Engels,  200. 

Enzyme,  hydrogenizing,  104. 
Enzymes,  103 
Equilibrium  between  oleic  and    stearic 

acid,  28. 
Erdmann,  8,  14,  19,  51,  60,  63,  64,  65, 

66,  67,  70,  72,  75,  79,  80,  117. 
Ernst,  103. 

Erucic  acid,  127,  196,  305. 
Eschweger  soap,  175,  176. 
Espil,  68. 

Ethylene,  11,  54,  86,  103. 
Eycken,  280. 

Fabris,  58,  113. 

Farmer,  33. 

Farnsteiner,  132. 

Fats,  animal,  98. 

Fatty  acids,  98,  180. 

Fatty  acids,  hardening  of,  49. 

Fatty  acids  of  hardened  oils,  132. 

Fatty  acids  of  stearin,  soaps  from,  71. 

Fatty  acids  of  Talgit,  133. 

Fatty  acids  of  tallow,  9. 

Fay,  54. 


INDEX 


331 


Fels  Naphtha  Soap  Works,  183. 

Ferment,  hydrogenizing,  104. 

Fiersot,  271. 

Fierz,  96. 

Filtration  of  oils  containing  nickel  from 

carbonyl,  97. 
Finely-divided  nickel,  82. 
Firth,  114,  120. 
Fischer,  271. 
Fish  oil,  25,  98,  104,  127,  128,  134,  161, 

163,  173,  305. 
Fish  oil,  Japanese,  79. 
Fish  oil,  nickel  in,  149. 
Flaky  form  of  nickel,  82. 
Foerster,  122. 

Foersterling  &  Philipp,  246. 
Fokin,  98,  105,  121,  139. 
Foods,    nickel    in,    when    prepared     in 

nickel  vessels,  149. 
Formate,  nickel,  67,  80. 
Formates  of  the  metals,  47. 
Formate,  zinc,  72. 
Formic  acid,  82,  107. 
Formic  acid  as  an  accelerator,  39. 
Formic  acid  as  a  source  of  hydrogen,  107. 
Fortini,  137. 
Franck,  77. 

Frank,  210,  211,  212,  215,  299. 
Freundlich,  3. 
Fry,  199. 
Fuchs,  40. 

Garth,  126,  163,  172. 

Garuti,  257,  265,  266,  267,  268. 

Gases,  diffusion  in  liquids,  199. 

Gates,  146. 

Gautier,  206,  215,  242. 

Geisenberger,  219. 

Gerard,  104. 

Gerhartz,  241. 

Germania  Olwerke,  163,  174,  188. 

German  patent  situation,  7-8. 

Gerum,  6. 

Giffard,  225. 

Glyceride,  stearic,  produced  by  hydro- 

genation,  64. 

Goldschmidt,  19,  199,  304. 
Grained  soap,  172. 
Grape  seed  oil,  39. 
Griesheim  Elektron  Co.,  196. 


Grimme,  134. 
Gruner,  33. 
Gutbier,  114. 

Hagemann,  82. 

Hahn,  206. 

Hajek,  181. 

Haleco,  173. 

Hall,  11,  152. 

Halla,  115. 

Haller,  11. 

Halphen  reaction,  98. 

Halphen  test,  127. 

Hardened  oil  fat  cleavage  reagent,  29. 

Hardened  oils,  keeping  qualities  of,  131. 

Hardened  oils,  unsaponifiable  constitu- 
ents of,  125. 

Hardening,  temperature  of,  39. 

Harmsen,  183. 

Hartmann,  6,  106. 

Hausaniann,  71. 

Hauser,  174. 

Hausmann,  21. 

Hautefeuille,  116. 

Hawes,  11. 

Hazard-Flamand,  285. 

Hefter,  1. 

Hehner,  313. 

Hembert,  203. 

Hemptinne,  3,  30,  31. 

Henry,  203. 

Herforder  Maschinenfett  und  Oelfabrik, 
7. 

Higgins,  39,  47,  52,  72,  82. 

Hildebrandt,  209. 

Hildesheimer,  85. 

Hills,  226. 

Hoitsema,  116. 

Holde,  195. 

Hollandsche  Residugas  Maatschappij, 
221. 

Holt,  114,  115. 

Hugel,  123,  126,  128,  147. 

Huston,  11. 

Hydrate,  nickel,  57. 

Hydride,  nickel,  116. 

Hydrik  process,  250. 

Hydrocarbon  oil,  11. 

Hydrocarbons,  decomposition  at  high 
temperatures,  56. 


332 


INDEX 


Hydrocarbons,  decomposition  of,  218, 
219. 

Hydrocarbons,  treatment  of,  21. 

Hydrogen  absorbed  by  various  metals, 
113. 

Hydrogen  by  the  action  of  acids  on 
metals,  243. 

Hydrogen  by  the  action  of  steam  on 
heated  metals,  225. 

Hydrogen  by  the  action  of  steam  on 
iron,  225. 

Hydrogen  by  decomposing  oils,  220. 

Hydrogen  by  decomposition  of  hydro- 
carbons, 217. 

Hydrogen  by  the  electrolysis  of  water, 
257. 

Hydrogen  circulation  system,  25. 

Hydrogen,  classification  of  methods  of 
making,  197. 

Hydrogen-containing  gases,  hydrogenat- 
ing  with,  198. 

Hydrogen  dioxide,  34. 

Hydrogen,  dry,  in  reducing  operations, 
69. 

Hydrogen  in  water  gas,  197. 

Hydrogen,  leakage  of,  194. 

Hydrogen,  light  activated,  33. 

Hydrogen,  miscellaneous  methods  of  gen- 
erating, 246. 

Hydrogen,  occlusion  of,  111. 

Hydrogen  pressure,  40,  79. 

Hydrogen,  preheating  in  fat  hardening, 
40. 

Hydrogen,  pressure  of,  19. 

Hydrogen,  pumping  of,  26. 

Hydrogen  purification,  297. 

Hydrogen,  reactions  with  oils,  196. 

Hydrogen  requirements  of  oils,  195. 

Hydrogen,  safety  devices,  292. 

Hydrogen,  summary  of  methods  of  mak- 
ing, 296. 

Hydrogen  under  pressure,  15. 

Hydrogen  under  pressure,  rate  of  hydro- 
genation,  122. 

Hydrogen,  waste,  196. 

Hydrogenated  butter  substitute,  153, 
154. 

Hydrogenated  oil,  assimilation  of,  145. 

Hydrogenated  oil,  fatty  acids  of,  180. 

Hydrogenated  oil  keeping  qualities,  158. 


Hydrogenated  oil  patent  litigation,  301. 
Hydrogenated   oils,    color   reactions   of, 

134. 
Hydrogenated  oils,  changes  taking  place 

in,  on  keeping,  147. 

Hydrogenated  oils,  resemblance  to  ani- 
mal fats,  132. 

Hydrogenating  hydrocarbon  oils,  20. 
Hydrogenating  oils  with  organic  salts  of 

nickel,  81. 

Hydrogenation  apparatus,  192. 
Hydrogenation  apparatus,  rotary  drum, 

32. 

Hydrogenation  by  catalytic  action,  5. 
Hydrogenation  by  stages,  24-25. 
Hydrogenation  not  affected  by  viscosity, 

35. 

Hydrogenation  of  hydrocarbon  oils,  21. 
Hydrogenation  of  oxidation  products  of 

oils,  39. 

Hydrogenating  oil  by  spraying,  12. 
Hydrogenating  oleic  acid,  13. 
Hydrogenation  practice,  191. 
Hydrogenation    process,    atomizing   oil, 

43. 
Hydrogenation   process,    dependent   on 

activity  of  catalyzers,  50. 
Hydrogenation  processes  involving  the 

application  of  electricity,  3. 
Hydrogenation  process  of  de  Kadt,  37. 
Hydrogenation     process     with     carrier 

metal  impregnated,  16. 
Hydrogenation  spraying  system,  76. 
Hydrogenation,  temperature  of,  39. 
Hydrogenation,   thermal    considerations 

in,  40. 

Hydrogenation  with  nickel  oxide  cata- 
lyzer, 61. 

Hydrogenit  process,  248. 
Hydrogenizing  ferment,  104. 
Hydrolecithin,  144. 
Hydroxy  fatty  acids,  19. 
Hydroxyl  group  destroyed   by   hydro- 

genation,  38. 
Hydroxyl  number,  126. 
Hydroxy-stearic  acid,  3,  196. 
Hypogaeic  acid,  133. 

Impregnated  catalyzer,  74. 
Indene,  58. 


INDEX 


333 


Index  of  refraction,  123,  130. 

Inductor  system,  26,  192. 

Inductor  system  of  hydrogenation,  48. 

Inner  iodine  number,  25. 

I.  O.  C.  system,  286. 

Iodine  number,  123. 

Iodine  number  of  liquid  fatty  acids,  25. 

Iodine  value,  130. 

Injector  apparatus,  36. 

Insulating  compositions,  159. 

Internationale  Wasserstoff  Aktien  Gesell- 

schaft,  236. 

International  Oxygen  Co.,  257,  281,  286. 
Ipatiew,  6,  19,  40,  50,  64. 
Iridium,  106. 
Iron,  39,  54. 
Iron  as  a  catalyzer,  79. 
Iron  formate,  72. 
Iron  oxide,  64. 
Iron  sponge  steam  process,  196. 

Jakowlew,  6. 
Japanese  fish  oil,  79. 
Japanese  sardine  oil,  127. 
Japanese  wood  oil,  121. 
Japan  wax,  soaps  of,  71. 
Jaubert,  241,  247,  248,  249,  251. 
Jenkins,  313. 
Jerzmanowski,  202. 
Jobling,  50. 
Jones,  103. 
Joslin,  144. 
Jouve,  215. 

Kalmus,  54. 
Kamps,  43. 
Kaolin,  121. 
Karl,  104. 
Kast,  70,  71. 
Kaya  oil,  157. 
Kayser,  15,  16,  73. 

Keeping  qualities  of  hardened  oils,  131. 
Kern,  119. 
Kerr,  138. 
Keutgen,  151. 

Kieselguhr,  16,  51,  73,'  75,  77. 
Kieselguhr  impregnated  with  nickel,  73. 
Kieselguhr,  objections  to,  82-83. 
Kieselguhr   saturated   with   nickel   car- 
bonyl,  43. 


Knapp,  129,  158. 

Knowles,  299. 

Knowles  Oxygen  Co.,  162. 

Kolbe,  5. 

Krebitz  process,  166. 

Krumhaar,  111. 

Krutolin,  184. 

Kuess,  3 

Lach,  183. 

Lactate,  nickel,  68. 

Lactates  of  the  metals,  47,  72. 

Lactones,  127. 

Lahousse,  253. 

Lake,  304. 

Lamplough,  21. 

Landis,  257. 

Lane,  226,  227,  228,  229. 

Langbein,  146. 

Langer,  52,  91,  96,  204. 

Lanthanum,  61. 

Lard  compound,  140. 

Lard  compound,  cost  of,  144. 

Lard  compound,  stability  of,  156. 

Lard  substitute,  140 

Latchinoff,  259. 

Laundry  soaps,  169. 

Lead  as  a  catalyzer,  21. 

Leakage  of  hydrogen  gas,  194. 

Leffer,  21. 

Lehmann,  67,  105,  145,  147. 

Leimdorfer,  134,  147,  169,  170. 

Lelarge,  294. 

Leprince  &  Siveke,  7,  173. 

Leprince  &  Siveke  patent,  7. 

Lepsius,  197. 

Leroy,  280. 

Lessing,  41. 

Lever  Bros.,  307. 

Levi,  202. 

Levin,  281. 

Lewes,  225. 

Lewkowitsch,  1,  123,  127,  313,  322. 

Lieber,  151. 

Liebmann,  311. 

Life  of  catalyzer,  55. 

Light,  use  of,  in  Walter's  process,  35. 

Linde,  195,  210,  211,  212. 

Linde-Caro  process,  43. 

Linde  Co.,  209. 


334 


INDEX 


Linde-Frank-Caro  system,  212. 

Linde  hydrogen  apparatus,  213. 

Lindt,  138. 

Linoleate,  nickel,  72,  80. 

Linoleic  acid,  130,  131,  305. 

Linolein,  24. 

Linolenic  acid,  131,  196. 

Linolic  acid,  130,  196,  305. 

Linolith,  188,  189,  190. 

Linseed  oil,  12,  39,  64,  81,  121,  124,  125, 

139,  160,  162,  188,  189,  190,  305. 
Linseed  oil  soaps,  188,  189,  190. 
Liquefaction  of  water  gas,  208. 
Litigation,  patent,  301. 
L'Oxhydrique  Francaise,  281. 
Long,  102. 

Loss  of  hydrogen,  26. 
Lubricants,  159. 
Luening,  271. 
Lysalbinic  acid,  101. 

Magnesium  oxide  as  a  carrier,  104. 

Magnier,  3. 

Mailhe,  5,  51. 

Majert,  253. 

Majima,  127. 

Manganese  as  a  catalyzer,  21. 

Marcusson,  25,  125. 

Marengo,  244. 

Maricheau-Beaupre,  252. 

Marie,  121. 

Markel  &  Crosfield,  38. 

Martha,  89. 

Maschinen-Anstalt  Humboldt,  213. 

Material,  candle,  179,  182. 

Mayer,  6,  65,  117,  125. 

McBain,  118. 

McCarty,  283. 

Mechanism  of  hydrogen  addition,  111. 

Meigen,  70. 

Meigen  &  Bartels,  9,  66. 

Mercury  chloride,  86. 

Messerschmitt,  230,  231,  232,  233,  234, 

235. 

Metal  oxides  as  catalyzers,  9. 
Metal  soaps,  40. 

Metals,  order  of  reducing  powers,  121. 
Metals,  reduction  of  oxides  to  metals,  54. 
Metallic  acetates,  47. 
Metallic  formates,  47. 


Metallic  lactates,  47. 

Metalloids  as  contact  poisons,  110. 

Methane,  53. 

Metropolitan  Laboratories,  45. 

Merz,  202. 

Meyer,  102,  109. 

Meyerheim,  25,  50,  125,  149. 

Mica  as  a  support,  107. 

Mineral  oil,  11. 

Mineral  oils,  polymerization  of,  31 . 

Miscellaneous     methods     of     hydrogen 

generation,  246. 
Moissan,  307,  309,  312,  321. 
Moist  hydrogen  in  hydrogenation,  69. 
Moisture,   a  cause  of  formation  of  free 

fatty  acids,  82. 
Moldenhauer,  203,  205,  239. 
Mond,  52,  88,  91,  92,  93,  94,  95,  96,  204. 
Mond  &  Langer  patent,  52. 
Moore,  61,  204. 
Moritz,  280,  281. 
Morris-Airey,  102. 
Moureu,  309. 

Muller,  131,  133,  147,  180,  205. 
Muller,  79. 
Munroe,  108. 

Naamlooze  Vennootschap  Ant.  Jurgen's 

Vereenigde  Fab.,  7,  74,  106. 
Naher,  205. 
Nasini,  92. 
Neville,  301. 

New  York  Oxygen  Co.,  202. 
Nickel,  39,  40,  53,  54,  121,  131. 
Nickel,  acetate,  68,  80. 
Nickel,  action  of,  114. 
Nickel  and  alumina,  53. 
Nickel  and  charcoal  catalyzer,  78. 
Nickel  as  a  test  for  hardened  oil,  130. 
Nickel,  benzildioxime  test  for,  138. 
Nickel  carbonyl,  20,  40,  41,  43,  69,  77, 

83,  88. 

Nickel  carbonyl,  properties  of,  89. 
Nickel  carbonyl  as  a  source  of  catalyzer, 

96. 
Nickel  carbonyl,   decomposition  in  oil, 

96. 
Nickel  carbonyl,  decomposition  of,  20,  90, 

95. 
Nickel  carbonyl,  preparation  of,  93. 


IXDKX 


335 


Nickel  carbonyl,  decomposition  under 
pressure,  96. 

Nickel  carbonyl,  heating  in  oil,  77. 

Nickel  carbonyl,  physiological  effect,  92. 

Nickel  carbonyl,  solvents  for,  90,  94. 

Nickel  catalyzer,  50,  51,  322. 

Nickel  catalyzer  affected  by  liquids,  13. 

Nickel  catalyzer,  handling  of,  192. 

Nickel  catalyzer  on  metal  support,  78. 

Nickel-cobalt  catalyzer,  70. 

Nickel  content  of  hydrogenated  oils, 
145. 

Nickel  electrodes,  5. 

Nickel  films,  83. 

Nickel,  finely-divided,  82. 

Nickel,  flaky  form  of,  82. 

Nickel  formate,  67,  72,  80,  82. 

Nickei  from  hypophosphite,  as  catalyzer, 
79. 

Nickel  hydrate,  57. 

Nickel  hydride,  116. 

Nickel  hypophosphite,  79. 

Nickel  in  fats  intended  for  edible  pur- 
poses, 145. 

Nickel  in  foodstuffs,  147. 

Nickel  hi  some  forms,  not  active,  67. 

Nickel  in  the  hardening  of  whale  oil,  50. 

Nickel,  Kerr's  test  for,  138. 

Nickel  iactate,  68. 

Nickel  linoleate,  72,  80. 

Nickel  mirror,  67. 

Nickel  oleate,  72,  80. 

Nickel  oxide,  19,  39,  40,  53,  54,  56,  57, 
60,  66,  67,  68,  70,  80,  117. 

Nickel  oxide,  activity  improved  by 
presence  of  other  metals,  61. 

^Nickel  oxide  catalyzer,  84. 

Nickel  oxide,  rate  of  hydrogenation  with, 
70. 

Nickel  oxide,  reduction  of,  54. 

Nickel  oxide  used  as  a  carrier,  77. 

Nickel  oxide  in  voluminous  form,  63. 

Nickel  oxides,  Boberg's  complex,  84. 

Nickel,  oxides  of  pyrophoric,  57. 

Nickel  powder,  41. 

Nickel,  precautions  to  prevent  contam- 
ination of  fat  by,  146. 

Nickel,  poisoning  of,  51. 

Nickel,  pyrophoric,  311. 

Nickel,  rate  of  hydrogenation  with,  70. 


Nickel,  reduced,  113. 

Nickel  resinate,  72. 

Nickel  salts,  organic,  67. 

Nickel  soaps,  62,  64,  71,  130,  173. 

Nickel  suboxide,  61,  64. 

Nickel,  tests  for,  137. 

Nickel,  tests  with  poison  squads  of,  147. 

Nickel,    treatment   of   fats    to   prevent 

solution  of,  149. 
Nickel  without  a  carrier,  83. 
Nickelized  pumice,  52. 
Nitrobenzol,  5. 
Nitrogen  Co.,  241. 
Nitrogen,  effect  on  catalyzer,  198. 
Noad,  11. 

Non-pyrophoric  catalyzer,  74,  122. 
Normann,  7-10,  123,  126,  128,  147,  182. 
Normann  patent,  7-10,  302. 
Normann  patent,  comments  of  Erdmann 

on,  8. 

Normann  process,  9. 
Norwegian  whale  oil,  162. 

Obach,  268. 

Occlusion  of  hydrogen,  111. 

Occlusion  of  hydrogen  by  nickel  oxide, 

117. 

Oechelhauser,  222. 
Oelwerke  Germania,  7. 
Oettli,  240. 
Offerdahl,  151. 
Ohmann,  293. 
Oil,  castor,  39,  98,   101,  104,   106,   121, 

125,  126,  139,  158,  160. 
Oil,  Chinese  wood,  162. 
Oil,  chrysalis,  162. 
Oil,  cocoanut,  124,  132,  133,  136,  140, 

152,  154,  156,  195. 
Oil,  cod  liver,  121. 
Oil,  corn,  124,  156,  195. 
Oil,  cottonseed,  20,  39,  41,  48,  65,  72,  76, 

79,  80,  82,  85,  97,  104,  123,  124,  125, 

132,  133,  149,  152,  305. 
Oil,  cottonseed,  nickel  in,  149. 
Oil,  Egyptian  cottonseed,  79. 
Oil,  filtration  of,  containing  nickel,  97. 
Oil,  fish,  98,  104,  127,  128,  134,  161,  163, 

305. 

Oil,  fish,  nickel  in,  149. 
Oil,  grapeseed,  39. 


336 


INDEX 


Oil-hardening  plants,  1. 

Oil-hardening  process,  32. 

Oil,  hydrogenated,  fatty  acids  of,  180. 

Oils,  hydrogenating,  192. 

Oil,  Japanese  fish,  79. 

Oil,  Japanese  sardine,  127. 

Oil,  Japanese  wood,  121. 

Oil,  Kaya,  157. 

Oil,  linseed,  39,  64,  81,   121,   124,   125, 

139,  162,  188,  189,  190,  305. 
Oil,  olive,  98,  100,  101, 105, 110, 195,  303, 

305. 

Oils,  oxidized,  124. 
Oil,  palm,  157. 
Oil,  peanut,  64,  106,  128,  132,  133,  136, 

145. 

Oil,  rape,  305. 
Oil-sealed  pump,  26. 
Oil,  sesame,  64,  124,  132,  136. 
Oil,  Soya  bean,  124,  154,  162. 
Oil,  sunflower,  162. 
Oil,  train,  174. 
Oil,  tung,  162. 
Oil,  whale,  39,  124,  126,  132,  134,  161, 

305. 

Oil,  wood,  162. 
Okada,  127. 
Oleate,  nickel,  72,  80. 
Oleic  acid,  70,   104,  106,  121,  195,  303, 

305. 
Oleic  acid,  behavior  in  the  Hemptinne 

process,  4. 

Oleic  acid,  electrical  reduction,  5. 
Oleic  acid,  hydrogenating  vapors  of,  12, 

26,  27,  28,  29. 
Oleic  acid,  reduction  in  iodine  number 

by  hydrogenation,  28. 
Oleic     and     stearic     acid,     equilibrium 

between,  28. 
Olein,  30,  196. 
Oleodistearin,  143. 
Oleodistearins,  isomeric,  144. 
Oleostearopalmitin,  144. 
Olive  oil,  98,  100,  101, 105,  110, 195,  303, 

305. 

Organic  compounds  of  metals,  72. 
Organic  salts  of  nickel,  81. 
Osann,  119. 
Osmium,  106. 
Osmium  dioxide,  colloidal,  105. 


Osmium  tetroxide,  67,  105. 

Oxidation  of  catalyzers,  prevention  of, 
74. 

Oxidation  products  of  oils,  hydrogena- 
tion of,  39. 

Oxide,  cobalt,  54,  64. 

Oxide,  iron,  64. 

Oxides,  metallic,  reduction  of,  54. 

Oxide,  nickel,  19,  56,  57,  60,  66,  67,  68, 
70,  117. 

Oxide,  nickel,  in  voluminous  form,  63. 

Oxides  of  pyrophoric  nickel,  57. 

Oxidized  oils,  124. 

Ozone  forming  electric  discharges,  44. 

Paal,  6,  98,  101,  104,  106,  108,  116. 
Padoa,  6,  58,  113. 
Palladious  hydroxide,  103. 
Palladium,  39,  79,  106,  107,  121. 
Palladium,  action  of  supporting  agents, 

104. 

Palladium,  active,  122. 
Palladium,  amorphous,  118. 
Palladium  black,  11,  41,  98,  122. 
Palladium  catalyzer,  7,  14,  21. 
Palladium  catalyzer,  poisoning  of,  14. 
Palladium  chloride,  99,  100. 
Palladium,  colloidal,  102. 
Palladium  electrodes,  5. 
Palladium  oil  colloids,  108. 
Palladium  oleate  organosols,  109. 
Palladium,  passive,  122. 
Palladium,  reaction  with  hydrogen,  115. 
Palladium  salts,  98,  105. 
Palladium,  spongy,  114. 
Palm  oil,  157,  162. 
Palmitic  acid,  3. 
Parker,  33. 

Passivity  of  metals,  122. 
Patent  litigation,  301. 
Patents  on  hydrogenation,  number  of,  7. 
Peanut-margarine,  136. 
Peanut-oleo,  136. 
Peanut  oil,  64,  106,  128,  132,  133,  136, 

145. 

Phorone,  116. 
Phillips,  20. 
Philipp,  247. 
Philipow,  6. 
Pfeilring  fat  cleavage  reagent,  29,  30. 


INDEX 


337 


Petroleum  oil,  11,  21. 
Petersen,  5,  121. 
Perl,  107. 
Perkin,  92. 

Physetoleic  acid,  133. 
Physiological  action  of  hardened  oils,  145. 
Phytosterol,  125,  126,  133,  136. 
Pictet,  217. 
Pilat,  21. 
Piva,  202. 

Platinum,  39,  106,  107, 121. 
•  Platinum  black,  98,  122. 
Platinum  black,  inactive  form,  115. 
Platinum  chloride,  98. 
Platinum  coated  on  metal,  78. 
Platinum  of  differing  activity,  115. 
Platinum  oil  colloids,  108. 
Platinum  salts,  105. 
Platinum  supported  on  asbestos,  108. 
Pleiss,  284. 

Poisons,  catalyzer,  14,  51,  54,  55,  305. 
Polymerization  of  mineral  oils,  31. 
Porter,  107. 
Poulsen  arc,  102. 
Prall,  130,  145. 
Pratis,  244. 
Preheating  hydrogen  in  fat  hardening, 

40. 

Preparation  of  catalyzer,  62. 
Preparation  of  colloidal  metals,  102. 
Pressure,  effect  of,  114. 
Pressure,  hydrogen,  40,  79. 
Pressure  of  hydrogen  affecting  rate  of 

conversion,  122. 
Pressure,  reduction  of,  promotes  hydro- 

genation,  36. 
Processes  involving  the  application  of 

electricity,  3. 
Process  involving  use  of  nickel  carbonyl, 

42. 

Proctor  &  Gamble  Co.,  16. 
Promoters  of  catalytic  action,  110. 
Protalbinic  acid,  101. 
Protective  colloid,  98,  100,  103. 
Pullman,  206. 

Pumice,  impregnated  with  nickel,  52. 
Pumice  stone,  51. 

Pure  hydrogen  for  fat  hardening,  199. 
Purification  of  hydrogen,  297. 
Pyrophoric  nickel,  311. 


Pyrophoric  nickel,  oxidation  and  reduc- 
tion of,  56. 

Pyrophoric  qualities  of  nickel,  over- 
coming the,  74. 

Quinke,  92. 

Rabenalt,  298. 

Rakitin,  6. 

Ramage,  304. 

Rancid  oil,  effect  of,  on  catalyzers,  43. 

Rape  oil,  127,  305. 

Rapid  hydrogenation,  23. 

Rapid  hydrogenation  with  stationary 
catalyzer,  23. 

Rare  metals  as  catalyzers,  98. 

Rays,  chemically  active,  41. 

Recovery  of  catalytic  material,  74. 

Recovery  of  catalyzer,  83. 

Reducible  metallic  salts  used  as  carriers, 
77. 

Reduction,  cathodic,  121. 

Reduction  coefficient,  68. 

Reduction  of  catalyzer,  continuous  meth- 
od, 86. 

Reduction  of  catalyzer,  87,  191. 

Reduction  of  nickel  catalytic  material, 
75,  76. 

Reduction  of  nickel  oxide,  54,  68. 

Reduction  of  nickel  oxide  in  oil,  9. 

Reduction  temperature  for  nickel  cata- 
lyzer, 51. 

Regenerating  spent  catalyzer,  74. 

Relative  reducing  powers  of  metals,  121. 

Renard,  260,  298. 

Revivification  of  catalyzer,  83. 

Reychler,  304. 

Rhead,  120. 

Rhodium,  106. 

Ribot,  175. 

Richards,  257. 

Richter,  21,  253. 

Ricinoleic  acid,  196,  305. 

Riedel,  144. 

Rincker,  219. 

Rosauer,  3. 

Rotary  drum  hydrogenation  apparatus, 
32. 

Roth,  6. 

Ruthenium,  106. 


338 


INDEX 


Sabatier,  11,  13,  29,  54,  56,  68,  116,  117, 

302,  307,  309,  321. 
Sabatier  and  Senderens,  5-6,  74. 
Sachs,  7. 

Safety  devices,  292. 
Sanders,  222. 

Saponification,  autoclave,  172. 
Saponification,  speed  of,  170. 
Saponification  value,  124. 
Saponin  powder,  190. 
Saubermann,  242. 
Sauer,  203. 
Sayteff,  5. 

Schaal,  166,  167,  175,  177. 
Schicht,  162. 
Schick,  107. 
Schiller,  11.  ; 

Schlinck,  H.  &  Co.,  21. 
Schmidt,  122,  257,  262. 
Schmidt  zinc  chloride  process,  3. 
Schoop,  257,  264,  265,  293. 
Schroeder,  63. 
Schuck,  174. 
Schuckert,  257,  272,  273,  274,  275,  276, 

277. 

Schwarz,  105. 
Schwartz,  247. 
Schwoerer,  12,  13. 
Seeker,  54. 

Selective  hydrogenation,  24-25. 
Semi-boiled  soaps,  170. 
Senderens,  7,  11,  13,  54,  56,  74,  302,  307. 
Sesame-margarine,  136. 
Sesame  oil,  64,  124,  132,  136. 
Sesame-oleo,  136. 
Settled  soap,  174. 
Shaving  soap,  169. 
Shaving  soaps,  177. 
Shaw,  26,  27,  28,  29. 
Sherieble,  44. 
Shriver  &  Co.,  262,  263. 
Shukoff,  20. 

Siemens  &  Schuckert  Co.,  250. 
Siemens  Bros.  &  Co.,  268. 
Siemens-Halske,  257. 
Sieverts,  111. 

Sieverts  &  Krumhaar,  111. 
Silica,  absorption  of,  by  catalyzers,  75. 
Silver,  61. 
Siveke,  7. 


Skita,  98,  100,  101,  106,  116. 

Sluggishness  of  catalyzers,  24. 

Soaps,  cocoanut  oil,  168. 

Soap,  copper,  71. 

Soaps,  discoloration  of,  173. 

Soap,  Eschweger,  175,  176. 

Soaps  from  hydrogenated  oil,  odor  of, 
169,  170,  172,  189. 

Soap,  grained,  172. 

Soap  industry,  hydrogenated  oils  in,  160. 

Soaps,  lathering  qualities,  169,  170,  172, 
190. 

Soaps,  laundry,  169. 

Soaps,  linseed,  188,  189,  190. 

Soap  made  with  Talgol,  164,  165,  166, 
167. 

Soaps,  metallic,  of  Japan  wax,  71. 

Soaps,  nickel,  62,  71,  130,  173. 

Soaps  of  heavy  metals,  40,  71. 

Soaps,  semi-boiled,  170. 

Soap,  settled,  174. 

Soap,  shaving,  169,  177. 

Soaps,  textile,  187. 

Soaps,  toilet,  170,  175. 

Soaps,  transparent  glycerine,  176. 

Societe  generate  des  Nitrures,  202. 

Sodium  oleate,  5. 

Sorption,  114,  118. 

Soya  bean  oil,  124,  154,  162. 

Specific  gravity,  change  of,  in  hydrocar- 
bon oils,  21. 

Specific  gravity  of  hardened  oils,  123. 

Speed  of  Saponification,  170. 

Spent  catalyzer,  action  of  acids  on,  75. 

Spongy  palladium,  114. 

Spraying  oil  in  hydrogenating,  18. 

Spraying  oil  in  hydrogenation  criticized, 

!     18. 

Stahlschmidt,  120. 

Stark,  105. 

Stationary  catalyzer,  22. 

Stearic  acid,  121,  196. 

Stearic  acid,  by  hydrogenating  vapor- 
ized oleic  acid,  26,  27,  28,  29. 

Stearic  acid  by  the  Hemptinne  process,  4. 

Stearic  and  oleic  acid,  equilibrium  be- 
tween, 28. 

Stearic  glycerides  in  hardened  oils,  130. 

Stearic  glyceride  produced  by  hydro- 
genation, 64. 


INDEX 


339 


Stearin,  30,  134,  174,  196. 
Stearin  market,  1. 

Stearin  produced  by  hydrogenation,  64. 
Stearin,  synthetic,  155. 
Stearin,  vegetable,  144. 
Steffan,  29. 
Sterols,  125,  126,  133. 
Stevens,  11. 
Strache,  238. 
Straub,  145. 

Suboxide,  nickel,  61,  64. 
Substances,  anticatalytic,  104. 
Substitute,  lard,  140. 
Sudfeldt  Brothers,  30. 
Sulfur  a  catalyzer  poison,  51,  54,  198/ 
Sulfur  containing  oils,  79. 
Sulfur  in  petroleum  oil,  11. 
Summary  of  methods  of  making  hydro- 
gen, 296. 

Sunflower  oil,  162. 
Sunlight  Soap  Factory,  162. 
Superhydrogenated  oil,  154. 
Surface  condensation,  119. 
Synthetic  stearin,  155. 

Talgin,  163. 

Talgit,  131,  133,  180. 

Talgol,  125,  126,  129,  163,  165,  169,  171, 

175,  178,  179. 
Tallow,  195. 

Tallow,  fatty  acids  of,  9,  303. 
Tanning  industry,  159. 
Tariff  on  hardened  oils,  183. 
Tchugaeff,  136. 
Techno-Chemical  Laboratories,  62,  76, 

303. 

Temperature  of  hydrogenation,  39. 
Temperature  of  reduction,  324. 
Tessie  du  Motay,  200. 
Testrup,  16-18,  303,  312. 
Textile  soaps,  187. 
Thermal  considerations  in  fat  hardening, 

40. 

Thompson,  115,  147,  161. 
Thorns,  147. 
Thron,  107. 
Tissier,  2,  3. 
Time,  effect  of,  in  hydrogenating  oleic 

acid,  28. 
Titanium,  61. 


Titoff,  120. 

Toilet  soaps,  170,  175. 

Tomassi,  119. 

Tommasini,  281. 

Train  oil,  174. 

Tran,  25. 

Transformation  of  oleic  to  stearic  acid,  1. 

Trinitrophenol,  71. 

Tristearine,  133,  183. 

Troost,  116. 

Tsujimoto,  161,  162. 

Tung  oil,  162. 

Turner,  11. 

Twitchell  process,  30. 

Ubbelohde,  12,  73. 

Ubbelohde  and  Goldschmidt,  1. 

Ueno,  157. 

Ultraviolet  light,  action  on  oils,  34. 

Unsaponifiable  constituents  of  hardened 

oils,  125. 

Uses  of  hydrogenated  oils,  159. 
Utescher,  33,  40. 
Uyeno,  252. 

Van  Scoyoc,  279. 

Vareille,  282. 

Varentrapp  reaction,  3. 

Vavon,  115. 

Vegetable  stearin,  144. 

Vereinigte  Chem.  Akt.  Ges.,  14,  29. 

Vereinigte  Chem.  Werke,  106. 

Vignon,  215,  240. 

Vieth,  151. 

Viscosity    not    affecting    hydrogenation 

rate,  35. 

von  Bergen,  105. 
von  Schonthan,  29. 

Wachtolf,  219. 

Walter,  34,  197. 

Wanz,  247. 

Waser,  5. 

Waste  hydrogen,  196. 

Water,  effect  on  fatty  acid  content,  82. 

Water,  electrolysis  of,  257. 

Water  gas,  10,  197,  199,  200. 

Water  gas,  liquefaction  of,  208. 

Weber,  169,  170,  178. 

Weinick,  3. 


340 


INDEX 


Weith,  202. 

Wentzki,  298. 

Whale  oil,  39,   124,  126,   132,   134,   161, 

305. 

Whale  oil,  edible  value  of  hardened,  149. 
Wheeler,  120. 
Wieland,  104. 

Wilbuschewitsch,  18,  46,  74,  75,  158. 
Wilhelmus,  189. 
Wilkinson,  11. 
Williams,  8,  12,  19,  64. 
Willstatter,  6,  125. 
Wimmer,  47,  50,  52,  72,  82. 
Wimmer  &  Higgins  process,  48. 


Windisch,  104,  105. 
Wolter,  219. 
Woltereck,  21. 
Wood  charcoal,  78,  120. 
Wood  oil,  162. 
Worms,  190. 
Woronin,  12,  73. 

Zinc  as  a  carrier,  104. 
Zinc  formate,  72. 
Zinc  oxide  as  a  carrier,  104. 
Zirconium,  61. 
Zirconium  oxide,  107. 
Zurrer,  2,  304. 


A  SELECTED  LIST  OF  BOOKS  ON 

CHEMISTRY      AND       CHEMICAL 
TECHNOLOGY 

Published  by 

D.    VAN    NOSTRAND    COMPANY 
25    Park    Place  New    York 


American  Institute  of  Chemical  Engineers.  Transactions. 
8vo.  cloth.  Issued  annually.  Vol.  L,  1908,  to  Vol. 
V.,  1912,  now  ready.  each,  net,  $6.00 

Annual  Reports  on  the  Progress  of  Chemistry.  Issued 
annually  by  the  Chemical  Society.  8vo.  cloth.  Vol.  I., 
1904,  to  Vol.  X.,  1913,  now  ready.  each,  net,  $2.00 

ASCH,  W.,  and  ASCH,  D.  The  Silicates  in  Chemistry  and 
Commerce.  Including  the  exposition  of  a  hexite  and 
pentite  theory  and  of  a  stereo-chemical  theory  of  gen- 
eral application.  Translated,  with  critical  notes  and 
additions,  by  Alfred  B.  Searle.  Illus.  6^4  x  10.  cloth. 
476  pp.  net,  $6.00 

BAILEY,  B.  0.  The  Brewer's  Analyst.  Illustrated.  8vo. 
cloth.  423  pp.  net,  $5.00 

BABKEB,  A.  F.,  and  MIDGLEY,  E.  Analysis  of  Woven 
Fabrics.  85  illustrations.  5/^x8^.  cloth.  319  pp. 

net,  $3.00 

BEADLE,  C.  Chapters  on  Papermaking.  Illustrated. 
I2mo.  cloth.  5  volumes.  •  each,  net,  $2.00 

BEAUMONT,  B.  Color  in  Woven  Design.  A  treatise  on 
the  science  and  technology  of  textile  coloring  (woolen, 
worsted,  cotton  and  silk  materials).  New  Edition,  re- 
written and  enlarged.  39  colored  plates.  367  illustra- 
tions. 8vo.  cloth.  369  pp.  net,  $6.00 


2  D.    VAN    NOSTRAND    COMPANY'S 

BECHHOLD,  H.  Colloids  in  Biology  and  Medicine. 
Translated  by  J.  G.  Bullowa,  M.D.  In  Press. 

BEEKMAN,  J.  M.    Principles  of  Chemical  Calculations. 

In  Press. 

BENNETT,  HUGH  G.  The  Manufacture  of  Leather, 
no  illustrations.  8vo.  cloth.  438  pp.  net,  $4.50 

BERNTHSEN,  A.  A  Text-book  of  Organic  Chemistry. 
English  translation.  Edited  and  revised  by  J.  J.  Sud- 
borowgh.  Illus.  i2mo.  cloth.  690  pp.  net,  $2.50 

BERSCH,  J.  Manufacture  of  Mineral  Lake  Pigments. 
Translated  by  A.  C.  Wright.  43  illustrations.  8vo. 
cloth.  476  pp.  net,  $5.00 

BEVERIDGE,  JAMES.  Papermaker's  Pocketbook.  Spe- 
cially compiled  for  paper  mill  operatives,  engineers, 
chemists  and  office  officials.  Second  and  Enlarged 
Edition.  Illus.  I2mo.  cloth.  211  pp.  net,  $4.00 

BIRCHMORE,  W.  H.  The  Interpretation  of  Gas  Analyses. 
Illustrated.  I2mo.  cloth.  75  pp.  net,  $1.25 

BLASDALE,  W.  C.  Principles  of  Quantitative  Analysis. 
An  introductory  course.  70  illus.  5>4X7/^-  cloth. 
404  pp.  net,  $2.50 

BLtfCHER,  H.  Modern  Industrial  Chemistry.  Trans- 
lated by  J.  P.  Millington.  Illus.  8vo.  cloth.  795 
pp.  net,  $7.50 

BLYTH,  A.  W.  Foods:  Their  Composition  and  Analysis. 
A  manual  for  the  use  of  analytical  chemists,  with  an 
introductory  essay  on  the  History  of  Adulterations. 
Sixth  Edition,  thoroughly  revised,  enlarged  and  re- 
written. Illustrated.  8vo.  cloth.  634  pp.  $7.50 

Poisons :  Their  Effects  and  Detection.     A  manual  for 

the  use  of  analytical  chemists  and  experts,  with  an 
introductory  essay  on  the  Growth  of  Modern  Toxicol- 
ogy. Fourth  Edition,  revised,  enlarged  and  rewritten. 
Illustrated.  8vo.  cloth.  772  pp.  $7.50 


LIST    OF    CHEMICAL    BOOKS 


B6CKMANN,  F.  Celluloid  ;  Its  Raw  Material,  Manufac- 
ture, Properties  and  Uses.  49  illustrations.  i2mo.  cloth. 
120  pp.  net,  $2.50 

BOOTH,  WILLIAM  H.  Water  Softening  and  Treatment. 
91  illustrations.  8vo.  cloth.  310  pp.  net,  $2.50 

BOURCART,  E.  Insecticides,  Fungicides,  and  Weed 
Killer?.  Translated  by  D.  Grant.  8vo.  cloth.  500  pp. 

net,  $4.50 

BOURRY,  EMILE.  A  Treatise  on  Ceramic  Industries. 
A  complete  manual  for  pottery,  tile,  and  brick  manu- 
facturers. A  revised  translation  from  the  French  by 
Alfred  B.  Searle.  308  illustrations.  12  mo.  cloth. 
488  pp.  net,  $5.00 

BRISLEE,  F.  J.  An  Introduction  to  the  Study  of  Fuel. 
A  text-book  for  those  entering  the  engineering,  chem- 
ical and  technical  industries.  60  ill.  8vo.  cloth.  293 
pp.  (Outlines  of  Industrial  Chemistry.)  net,  $3.00 

BRUCE,  EDWIN  M.  Detection  of  the  Common  Food 
Adulterants.  Illus.  i2mo.  cloth.  90  pp.  net,  $1.25 

BUSKETT,  E.  W.  Fire  Assaying.  A  practical  treatise  on 
the  fire  assaying  of  gold,  silver  and  lead,  including 
descriptions  of  the  appliances  used.  Illustrated.  I2mo. 
cloth.  ii2  pp.  net,  $1.25 

BYERS,  HORACE  G.,  and  KNIGHT,  HENRY  G.  Notes 
on  Qualitative  Analysis.  Second  Edition,  revised. 
8vo.  cloth.  192  pp.  net,  $1.50 

CAVEN,  R.  M.,  and  LANDER,  G.  D.  Systematic  Inor- 
ganic Chemistry  from  the  Standpoint  of  the  Periodic 
Law.  A  text-book  for  advanced  students.  Illustrated. 
i2mo.  cloth.  390  pp.  net,  $2.00 

CHRISTIE,  W.  W.  Boiler-waters,  Scale,  Corrosion,  Foam- 
ing. 77  illustrations.  8vo.  cloth.  242  pp.  net,  $3.00 

Water,  Its  Purification  and  Use  in  the  Industries. 

79  illus.,  3  folding  plates,  2  colored  inserts.  i2mo. 
cloth.  230  pp.  net,  $2.00 


4  D.    VAN   NOSTRAND    COMPANY'S 

CHURCH'S  Laboratory  Guide.  A  manual  of  practical 
chemistry  for  colleges  and  schools,  specially  arranged 
for  agricultural  students.  Ninth  Edition,  revised  and 
partly  rewritten  by  Edward  Kinch.  Illustrated.  8vo. 
cloth,  365  pp.  net,  $2.50 

CORNWALL,  H.  B.  Manual  of  Blow-pipe  Analysis. 
Qualitative  and  quantitative.  With  a  complete  system 
of  determinative  mineralogy.  Sixth  Edition,  revised. 
70  illustrations.  8vo.  cloth.  310  pp.  net,  $2.50 

CROSS,  C.  F.,  BEVAN,  E.  J.,  and  SINDALL,  R.  W. 
Wood  Pulp  and  Its  Uses.  With  the  collaboration  of 
W.  N.  Bacon.  30  illustrations.  I2mo.  cloth.  281 
pp.  (Van  Nostrand's  Westminster  Series.)  net,  $2.00 

d'ALBE,  E.  E.  F.  Contemporary  Chemistry.  A  survey 
of  the  present  state,  methods,  and  tendencies  of  chemi- 
cal science.  I2mo.  cloth.  172  pp.  net,  $1.25 

DANBY,  ARTHUR.  Natural  Rock  Asphalts  and  Bitu- 
mens. Their  Geology,  History,  Properties  and  Indus- 
trial Application.  Illustrated.  I2mo.  cloth.  254  pp. 

net,  $2.50 

DEERR,  N.  Sugar  and  the  Sugar  Cane.  280  illustra- 
tions. 6^x9%.  cloth.  608  pp.  net,  $8.00 

DUMESNY,  P.,  and  NOYER,  J.  Wood  Products,  Dis- 
tillates and  Extracts.  Translated  by  D.  Grant.  103 
illustrations.  8vo.  cloth.  320  pp.  net,  $4.50 

DUNSTAN,  A.  E.,  and  THOLE,  F.  B.  A  Text-book  of 
Practical  Chemistry  for  Technical  Institutes.  52  illus- 
trations. I2mo.  cloth.  345  pp.  net,  $1.40 

DYSON,  S.  S.,  and  CLARKSON,  S.  S.  Chemical  Works, 
Their  Design,  Erection,  and  Equipment.  80  illustra- 
tions, 9  folding  plates.  8vo.  cloth.  220  pp.  net,  $7.50 

ELIOT,  C.  W.,  and  STORER,  F.  H.  A  Compendious  Man- 
ual of  Qualitative  Chemical  Anatyais.  Revised  with 


LIST    OF    CHEMICAL   BOOKS 


the  co-operation  of  the  authors,  by  William  R. 
Nichols.  Twenty-second  Edition,  newly  revised  by 
W.  B.  Lindsay.  111.  I2mo.  cloth.  205  pp.  net,  $1.25 

ELLIS,  C.  Hydrogenation  of  Oils,  Catalysis  and  Catalyzers, 
and  the  Generation  of  Hydrogen.  145  ill.  6x9.  cloth. 
350  pp.  net,  $4.00 

ENNIS,  WILLIAM  D.  Linseed  Oil  and  Other  Seed  Oils. 
An  industrial  manual.  88  illustrations.  8vo.  cloth. 
336  pp.  net,  $4.00 

ERMEN,  W.  F.  A.  The  Materials  Used  in  Sizing.  Their 
chemical  and  physical  properties,  and  simple  methods 
for  their  technical  analysis  and  valuation.  Illustrated. 
I2mo.  cloth.  130  pp.  net,  $2.00 

FAY,  IRVING  W.  The  Chemistry  of  the  Coal-tar  Dyes. 
8vo.  cloth.  473  pp.  net,  $4.00 

FERNBACH,  R.  L.  Chemical  Aspects  of  Silk  Manu- 
facture. 121110.  cloth.  84  pp.  net,  $1.00 

'Glue  and  Gelatine.  A  practical  treatise  on  the 

methods  of  testing  and  use.  Illustrated.  8vo.  cloth. 
208  pp.  net,  $3.00 

FISCHER,  E.  Introduction  to  the  Preparation  of  Or- 
ganic Compounds.  Translated  from  the  new  (eighth) 
German  edition  by  R.  V.  Stanford.  Illustrated. 
I2mo.  cloth.  194  pp.  net,  $1.25 

FO YE,  J.  C.  Chemical  Problems.  Fourth  Edition,  revised 
and  enlarged,  i6mo.  cloth.  145  pp.  (Van  Nos- 
trand  Science  Series,  No.  69.)  $0.50 

FRANZEN,  H.  Exercises  in  Gas  Analysis.  Translated 
from  the  first  German  edition,  with  corrections  and 
additions  by  the  author,  by  Thomas  Callan.  30  dia- 
grams. 5x7^4.  cloth.  127  pp.  net,  $1.00 

FRITSCH,  J.  The  Manufacture  of  Chemical  Manures. 
Translated  from  the  French,  with  numerous  notes,  by 
Donald  Grant.  69  illus.,  108  tables.  8vo.  cloth. 
355  pp.  net,  $4.00 


6  D.   VAN  NOSTRAN-D  COMPANY'S 

GROSSMANN,  J.  Ammonia  and  Its  Compounds.  Illus- 
trated. I2mo.  cloth.  151  pp.  net,  $1.25 

HALE,  WILLIAM  J.  Calculations  in  General  Chemistry. 
With  definitions,  explanations  and  problems.  Second 
Edition,  revised.  I2mo.  cloth.  185  pp.  net,  $1.00 

HALL,  CLARE  H.  Chemistry  of  Paints  and  Paint  Ve- 
hicles. 8vo.  cloth.  141  pp.  •  net,  $2.00 

HILDITCH,  T.  P.  A  Concise  History  of  Chemistry. 
1 6  diagrams.  I2mo.  cloth.  273  pp.  net,  $1.25 

HOPKINS,  N.  M.  Experimental  Electrochemistry :  Theo- 
retically and  Practically  Treated.  132  illustrations. 
8vo.  cloth.  298  pp.  net,  $3.00 

HOULLEVIGUE,  L.  The  Evolution  of  the  Sciences. 
8vo.  cloth.  377  pp.  net,  $2.00 

HtJBNER,  JULIUS.  Bleaching  and  Dyeing  of  Vegetable 
Fibrous  Materials.  95  illus.  (many  in  two  colors). 
8vo.  cloth.  457  pp.  (Outlines  of  Industrial  Chem- 
istry.) net,  $5.00 

HUDSON,  0.  F.  Iron  and  Steel.  An  introductory  text- 
book for  engineers  and  metallurgists.  With  a  section 
on  Corrosion  by  Guy  D.  Bengough.  47  illus.  8vo. 
cloth.  184  pp.  (Outlines  of  Industrial  Chemistry.) 

net,  $2.00 

HURST,  GEO.  H.  Lubricating  Oils,  Fats  and  Greases. 
Their  origin,  preparation,  properties,  uses,  and  analy- 
sis. Third  Edition,  revised  and  enlarged,  by  Henry 
Leask.  74  illus.  8vo.  cloth.  405  p.  net,  $4.00 

HYDE,  FREDERIC  S.  Solvents,  Oils,  Gums,  Waxes  and 
Allied  Substances.  5^x^-  cloth.  182  pp. 

net,  $2.00 

INGLE,  HERBERT.  Manual  of  Agricultural  Chemistry. 
Illustrated.  8vo.  cloth.  388  pp.  net,  $3.00 


LIST    OF    CHEMICAL    BOOKS 


JOHNSTON,  J.  F.  W.  Elements  of  Agricultural  Chem- 
istry. Revised  and  icwritten  by  Charles  A.  Cameron 
and  C.  M.  Aikman.  Nineteenth  Edition.  Illustrated. 
I2mo.  cloth.  502  pp.  $2.60 

JONES,  HARRY  C.  A  New  Era  in  Chemistry.  Some  of 
the  more  important  developments  in  general  chemis- 
try during  the  last  quarter  of  a  century.  Illustrated. 
121110.  cloth.  336  pp.  net,  $2.00 

XEMBLE,  W.  F.,  and  UNDERBILL,  C.  R.  The  Periodic 
Law  and  the  Hydrogen  Spectrum.  Illustrated.  8vo. 
paper.  16  pp.  net,  $0.50 

KERSHAW,  J.  B.  C.  Fuel,  Water,  and  Gas  Analysis,  for 
Steam  Users.  50  ill.  8vo.  cloth:  178  pp.  net,  $2.50 
-  Electro-Thermal  Methods  of  Iron  and  Steel  Produc- 
tion. With  an  introduction  by  Dr.  J.  A.  Fleming, 
F.R.S.  .50  tables,  92  illustrations.  53/2x8^4.  cloth. 
262  pp.  net,  $3.00 

KNOX,  JOSEPH.  Physico-chemical  Calculations.  i2mo. 
cloth.  196  pp.  net,  $1.00 

KOLLER,  T.  Cosmetics.  A  handbook  of  the  manufac- 
ture, employment  and  testing  of  all  cosmetic  materials 
and  cosmetic  specialties.  Translated  from  the  German 
by  Charles  Salter.  8vo.  cloth.  262  pp.  net,  $2.50 

KREMANN,  R.  The  Application  of  Physico-chemical 
Theory  to  Technical  Processes  and  Manufacturing 
Methods.  Authorized  translation  by  Harold  E.  Potts, 
M.Sc.  35  diagrams.  8vo.  cloth.  215  pp.  net,  $2.50 

KRETSCHMAR,  KARL.  Yarn  and  Warp  Sizing  in  All 
Its  Branches.  Translated  from  the  German  by  C. 
Salter.  122  illus.  Svo.  cloth.  192  pp.  net,  $4.00 

LAMBORN,  L.  L.     Modern  Soaps,  Candles  and  Glycerin. 

224  illustrations.     Svo.     cloth.     700  pp.         net,  $7.50 

-Cotton  Seed  Products.     79  illus.  Svo.  cloth.  253  pp. 

net,  $3.00 


8  D.    VAN   NOSTRAND    COMPANY'S 

LASSAR-COHN.  Introduction  to  Modern  Scientific 
Chemistry.  In  the  form  of  popular  lectures  suited  for 
University  Extension  students  and  general  readers. 
Translated  from  the  Second  German  Edition  by  M.  M. 
Pattison  Muir.  Illus.  I2mo.  cloth.  356  pp.  $2.00 

LETTS,  E.  A.  Some  Fundamental  Problems  in  Chemis- 
try :  Old  and  New.  44  illustrations.  8vo.  cloth.  236 
pp.  net,  $2.00 

LUNGE,  GEORGE.  Technical  Methods  of  Chemical 
Analysis.  Translated  from  the  Second  German  Edition 
by  Charles  A.  Keane,  with  the  collaboration  of  eminent 
experts.  To  be  complete  in  three  volumes. 
Vol.  I.  (in  two  parts).  201  illustrations.  Svo.  cloth. 
1024  pp.  net,  $15.00 

Vol.  II.   (in  two  parts).     Illus.     6^x9.     1294 pp. 

net,  $18.00 
Vol.  III.  in  active  preparation. 

Technical  Chemists'  Handbook.  Tables  and  meth- 
ods of  analysis  for  manufacturers  of  inorganic  chemi- 
cal products.  Illus.  I2mo.  leather.  276  pp.  net,  $3.50 
Coal,  Tar  and  Ammonia.  Fourth  and  Enlarged  Edi- 


tion, In  two  volumes,  not  sold  separately.  305  illus- 
trations. Svo.  cloth.  1210  pp.  net,  $15.00 

The   Manufacture   of   Sulphuric   Acid   and   Alkali. 

A  theoretical  and  practical  treatise. 
Vol.   I.     Sulphuric  Acid.     Fourth  Edition,  enlarged. 
In  three  parts,  not  sold  separately.     543  illustrations. 
8vo.     cloth.     1665  pp.  net,  $18.00 

Vol.  II.  Sulphate  of  Soda,  Hydrochloric  Acid,  Leblanc 
Soda.  Third  Edition,  much  enlarged.  In  two  parts, 
not  sold  separately.  335  illustrations.  Svo.  cloth. 
1044  pp.  net>  $15.00 

Vol.  III.    Ammonia  Soda.    Various  Processes  of  A1- 


LIST    OF    CHEMICAL   BOOKS  9 

kali-making,  and  the  Chlorine  Industry.  181  illus- 
trations. 8vo.  cloth.  784  pp.  net,  $10.00 
Vol.  IV.  Ele.ctrol ytical  Methods.  In  Press. 

McINTOSH,  JOHN  G.  The  Manufacture  of  Varnish  and 
Kindred  Industries.  Illus.  8vo.  cloth.  In  3  volumes. 
Vol.  I.  Oil  Crushing,  Refining  and  Boiling;  Manu- 
facture of  Linoleum ;  Printing  and  Lithographic  Inks ; 
India  Rubber  Substitutes.  29  illus.  160  pp.  net,  $3.50 
Vol.  II.  Varnish  Materials  and  Oil  Varnish  Making. 
66  illus.  216  pp.  net,  $4.00 

Vol.  III.  Spirit  Varnishes  and  Varnish  Materials. 
64  illus.  492  pp.  net,  $4.50 

MARTIN,  G.  Triumphs  and  Wonders  of  Modern  Chem- 
istry. A  popular  treatise  on  modern  chemistry  and 
its  marvels  written  in  non-technical  language.  76  il- 
lustrations. I2mo.  cloth.  358  pp.  net,  $2.00 

MELICK,  CHARLES  W.  Dairy  Laboratory  Guide.  52 
illustrations.  I2mo.  cloth.  135  pp.  net,  $1.2? 

MERCK,  E.  Chemical  Reagents :  Their  Purity  and  Tests. 
Second  Edition,  revised.  6x9.  cloth.  210  pp.  $1.00 

MIERZINSKI,  S.  The  Waterproofing  of  Fabrics.  Trans- 
lated from  the  German  by  A.  Morris  and  H.  Robson. 
Second  Edition,  revised  and  enlarged.  29  illustrations. 
5x7^.  140  pp.  net,  $2.50 

MITCHELL,  C.  A.  Mineral  and  Aerated  Waters,  in 
illustrations.  8vo.  cloth.  244  pp.  net,  $3.00 

MITCHELL,  C.  A.,  and  PRIDEAUX,  R.  M.  Fibres  Used 
in  Textile  and  Allied  Industries.  66  illustrations. 
8vo.  cloth.  208  pp.  net,  $3.00 

MUNBY,  A.  E.  Introduction  to  the  Chemistry  and 
Physics  of  Building  Materials.  Illus.  8vo.  cloth.  365 
pp.  (Van  Nostrand's  Westminster  Series.)  net,  $2.00 

MURRAY,  J.  A.  Soils  and  Manures.  33  illustrations. 
8v6.  cloth.  367  pp.  (Van  Nostrand's  Westminster 
Series.)  net,  $2.00 


io  D.  VAN  NOSTRAND  COMPANY'S 

NAQUET,  A.  Legal  Chemistry.  A  guide  to  the  detec- 
tion of  poisons  as  applied  to  chemical  jurisprudence. 
Translated,  with  additions,  from  the  French,  by  JV  P. 
Battershall.  Second  Edition,  revised  with  additions. 
I2mo.  cloth.  190  pp.  $2.00 

NEAVE,  G.  B.,  and  HEILBRON,  I.  M.  The  Identifica- 
tion of  Organic  Compounds.  i2mo.  cloth,  in  pp. 

net,  $1.25 

NORTH,  H.  B.  Laboratory  Experiments  in  General 
Chemistry.  Second  Edition,  revised.  36  illustrations. 
5>4X7M-  cloth.  212  pp.  net,  $1.00 

OLSEN,  J.  C.  A  Textbook  of  Quantitative  Chemical 
Analysis  by  Gravimetric  and  Gasoinetric  Methods. 
Including  74  laboratory  exercises  giving  the  analysis 
of  pure  salts,  alloys,  minerals  and  technical  products. 
Fourth  Edition,  revised  and  enlarged.  74  illustrations. 
8vo.  cloth.,  576  pp.  net,  $4.00 

PAKES,  W.  C.  G.,  and  NANKIVELL,  A.  T.  The  Science 
of  Hygiene.  A  text-book  of  laboratory  practice.  80 
illustrations.  i2mo.  cloth.  175  pp.  net,  $1.75 

PARRY,  ERNEST  J.  The  Chemistry  of  Essential  Oils 
and  Artificial  Perfumes.  Second  Edition,  thoroughly 
revised  and  greatly  enlarged.  Illustrated.  8vo.  cloth. 
554  pp.  net,  $5.00 

Food  and  Drugs.     In  2  volumes.    Illus.    8vo.  cloth. 

Vo!.  I.     The  Analysis  of  Food  and  Drugs   (Chemical 
and  Microscopical).    59  illus.    724  pp.  net,  $7.50 

Vol.   II.     The  Sale  of  Food  and  Drugs  Acts,   1873- 
1907.     184  pp.  net,  $3.00 

PARTINCirON,  JAMES  R.  A  Text-book  of  Thermo- 
dynamics (with  special  reference  to  Chemistry).  91 
diagrams.  8vo.  cloth.  550  pp.  net,  $4.00 

-• Higher    Mathematics    for    Chemical    Students.      44 

diagrams.     i2mo.     cloth.     272  pp.  net,  $2.00 


LIST    OF    CHEMICAL   BOOKS  n 

PERKIN,  F.  M.  Practical  Methods  of  Inorganic  Chem- 
istry. Illustrated.  i2mo.  cloth.  152  pp.  net,  $1.00 

PHILLIPS,  J.  Engineering  Chemistry.  A  practical 
treatise.  Comprising  methods  of  analysis  and  valua- 
tion of  the  principal  materials  used  in  engineering 
works.  Third  Edition,  revised  and  enlarged.  Illus- 
trated. i2mo.  cloth.  422  pp.  net,  $4.50 

PLATTNER'S  Manual  of  Qualitative  ai/d  Quantitative 
Analysis  with  the  Blowpipe.  Eighth  Edition,  revised. 
Translated  by  Henry  B.  Cornwall,  assisted  by  John 
H.  Caswell,  from  the  Sixth  German  Edition,  by  Fried- 
rich  Kolbeck.  87  ill.  8vo.  cloth.  463  pp.  net,  $4.00 

POLLEYN,  F.  Dressings  and  Finishings  for  Textile 
Fabrics  and  Their  Application.  Translated  from  the 
Third  German  Edition  by  Chas.  Salter.  60  illustra- 
tions. 8vo.  cloth.  279  pp.  net,  $3.00 

POPE,  F.  Gr.  Modern  Research  in  Organic  Chemistry. 
261  diagrams.  I2mo.  cloth.  336  pp.  net,  $2.25 

PORRITT,  B.  D.  The  Chemistry  of  Rubber.  5x7^. 
cloth.  100  pp.  (Van  Nostrand's  Chemical  Mono- 
graphs, No.  3.)  net,  $0.75 

POTTS,  HAROLD  E.  Chemistry  of  the  Rubber  Industry. 
8vo.  cloth.  163  pp.  (Outlines  of  Industrial  Chem- 
istry.) net,  $2.00 

PRESCOTT,  A.  B.  Organic  Analysis.  A  manual  of  the 
descriptive  and  analytical  chemistry  of  certain  carbon 
compounds  in  common  use.  Sixth  Edition.  Illus- 
trated. 8vo.  cloth.  533  pp.  $5.00 

PRESCOTT,  A.  B.,  and  JOHNSON,  0.  C.  Qualitative 
Chemical  Analysis.  Sixth  Edition,  revised  and  en- 
larged. 8vo.  cloth.  439  pp.  net,  $3.50 

PRESCOTT,  A.  B.,  and  SULLIVAN,  E  C.  First  Book  in 
Qualitative  Chemistry.  For  studies  of  water  solution 
and  mass  action.  Eleventh  Edition,  entirely  rewritten. 
i2mo.  cloth.  150  pp.  net,  $1.50- 


12         D.    VAN    NOSTRAND    COMPANY'S 

PRIDEAUX,  E.  B.  R.  Problems  in  Physical  Chemistry 
with  Practical  Applications.  13  diagrams.  8vo.  cloth. 
323  pp.  net,  $2.00 

PROST,  E.  Manual  of  Chemical  Analysis.  As  applied 
to  the  assay  of  fuels,  ores,  metals,  alloys,  salts,  and 
other  mineral  products.  Translated  from  the  original 
by  J.  C.  Smith.  Illus.  Svo.  cloth.  300  pp.  net,  $4.50 

PYNCHON,  T.  R.  Introduction  to  Chemical  Physics. 
Third  Edition,  revised  and  enlarged.  269  illustrations. 
Svo.  cloth.  575  pp.  $3.00 

RICHARDS,  W.  A.,  and  NORTH,  H.  B.     A  Manual  of 
Cement  Testing.      For  the  use  of  engineers  and  chem- 
ists   in   colleges   and    in   the   field.      56   illustrations. 
I2mo.     cloth.      147  pp.  net,  $1.50 

ROGERS,  ALLEN.  A  Laboratory  Guide  of  Industrial 
Chemistry.  Illustrated.  Svo.  cloth.  170  pp.  net,  $1.50 

ROGERS,  ALLEN,  and  AUBERT,  ALFRED  B.  (Editors.) 
Industrial  Chemistry.  A  manual  for  the  student  and 
manufacturer.  Written  by  a  staff  of  eminent  special- 
ists. 340  illus.  Svo.  cloth.  872  pp.  net,  $5.00 

ROHLAND,  PAUL.  The  Colloidal  and  Crystalloidal  State 
of  Matter.  Translated  by  W.  J.  Britland  and  H.  E. 
Potts.  I2mo.  cloth.  54  pp.  net,  $1.25 

ROTH,  W.  A.  Exercises  in  Physical  Chemistry.  Author- 
ized translation  by  A.  T.  Cameron.  49  illustrations. 
Svo.  cloth.  208  pp.  net,  $2.00 

SCHERER,  R.  Casein:  Its  Preparation  and  Technical 
Utilization.  Translated  from  the  German  by  Charles 
Salter.  Second  Edition,  revised  and  enlarged.  Il- 
lustrated. Svo.  cloth.  196  pp.  net,  $3.00 

SCHIDROWITZ,  P.  Rubber.  Its  Production  and  Indus- 
trial Uses.  Plates,  83  illus.  Svo.  cloth.  320  pp. 

net,  $5.00 

SCHWEIZER,  V.  Distillation  of  Resins,  Resinate  L~-k<-> 
and  Pigments.  Illustrated.  Svo.  cloth,  i83pp.net,  $3.50 


LIST    OP    CHEMICAL   BOOKS  13 

SCOTT,  W.  W.  Qualitative  Chemical  Analysis.  A  labo- 
ratory manual.  Second  Edition,  thoroughly  revised. 
Illtis.  8vo.  cloth.  180  pp.  net,  $1.50 

SCUDDER,  HEYWARD.  Electrical  Conductivity  and 
lonizatiofl  Constants  of  Organic  Compounds.  6x9. 
cloth.  575  pp.  net,  $3.00 

SEARLE,  ALFRED  B.  Modern  Brickmaking.  260  illus- 
trations. 8vo.  cloth.  449  pp.  net,  $5.00 

Cement,    Concrete    and    Bricks.       113    illustrations. 

Sy2  x8}4.    cloth.    415  pp.  net,  $3.00 

SEIDELL,  A.  Solubilities  of  Inorganic  and  Organic  Sub- 
stances. A  handbook  of  the  most  reliable  quantitative 
solubility  determinations.  Second  Printing,  corrected. 
8vo.  cloth.  367  pp.  net,  $3.00 

SENTER,  G.  Outlines  of  Physical  Chemistry.  Second 
Edition,  revised.  Illus.  I2mo.  cloth.  401  pp.  $1.75 

A  Text-book  of  Inorganic  Chemistry.  90  illustra- 
tions. i2mo.  cloth.  595  pp.  net,  $1.75 

SEXTON,  A.  H.  Fuel  and  Refractory  Materials.  Second 
Ed.,  revised.  104  illus.  I2mo.  cloth.  374pp.  net,  $2.00 

Chemistry  of  the  Materials  of  Engineering.  Illus. 

I2mo.  cloth.  344  pp.  net,  $2.50 

SIMMONS,  W.  H.,  and  MITCHELL,  C.  A.  Edible  Fats 
and  Oils.  Their  composition,  manufacture  and  analy-- 
sis.  Illustrated.  8vo.  cloth.  164  pp.  net,  $3.00 

SINDALL,  R.  W.  The  Manufacture  of  Paper.  58  illus. 
8vo.  cloth.  285  pp  .  (Van  Nostrand's  Westminster 
Series.)  net,  $2.00 

SINDALL,  R.  W.,  and  BACON,  W.  N.  The  Testing  of 
Wood  Pulp.  A  practical  handbook  for  the  pulp  and 
paper  trades.  Illus.  8vo.  cloth.  150  pp.  net,  $2.50 


i4         D.    VAN   NOSTRAND    COMPANY'S 

SMITH,  W.  The  Chemistry  of  Hat  Manufacturing. 
Revised  and  edited  by  Albert  Shonk.  Illustrated. 
I2mo.  cloth.  132  pp.  net,  $3.00 

SOUTHCOMBE,  J.  E.  Chemistry  of  the  Oil  Industries, 
lllus.  8vo.  cloth.  209  pp.  (Outlines  of  Industrial 
Chemistry.)  net,  $3.00 

SPEYERS,  C.  L.  Text-book  of  Physical  Chemistry.  20 
illustrations.  8vo.  cloth.  230  pp.  net,  $2.25 

STEVENS,  H.  P.  Paper  Mill  Chemist.  67  illustrations. 
82  tables.  i6mo.  cloth.  280  pp.  net,  $2.50 

SUDBOROUGH,  J.  J.,  and  JAMES,  J.  C.  Practical  Or- 
ganic Chemistry.  92  illustrations.  i2mo.  cloth. 
394  pp.  net,  $2.00 

TERRS',  H.  L.  India  Rubber  and  Its  Manufacture. 
1 8  illustrations.  8vo.  cloth.  303  pp.  (Van  Nos- 
trand's  Westminster  Series.)  net,  $2.00 

TITHERLEY,  A.  W.  Laboratory  Course  of  Organic 
Chemistry,  Including  Qualitative  Organic  Analysis. 
Illustrated.  8vo.  cloth.  235  pp.  net,  $2.00 

TOCH,  M.  Chemistry  and  Technology  of  Mixed  Paints. 
New  Edition,  in  two  volumes.  In  Preparation. 

TOCH,  M.  Materials  for  Permanent  Painting.  A  manual 
for  manufacturers,  art  dealers,  artists,  and  collectors. 
With  full-page  plates..  Illustrated.  i2mo.  cloth. 
208  pp.  net,  $2.00 

TUCKER,  J.  H.  A  Manual  of  Sugar  Analysis.  Sixth 
Edition.  43  illustrations.  Svo.  cloth.  353  pp.  $3.50 

UNDERWOOD,  N.,  and  SULLIVAN,  T.  V.  Chemistry  and 
Technology  of  Printing  Inks.  In  Press. 

VAN  NOSTRAND'S  Chemical  Annual.  Edited  by  John 
C.  Olsen  and  Alfred  Melhado.  A  handbook  of  useful 
data  for  analytical  manufacturing  and  investigating 


LIST    OF    CHEMICAL   BOOKS  15 

chemists  and  chemical  students.   Third  Issue,  enlarged. 
5x7^2.    leather.    683  pp.  net,  $2.50 

VINCENT,  C.  Ammonia  and  Its  Compounds.  Their 
manufacture  and  uses.  Translated  from  the  French 
by  M.  J.  Salter.  32  ill.  8vo.  cloth.  113  pp.  net,  $2.00 

VON  GEORGIEVICS,  G.  Chemical  Technology  of  Textile 
Fibres.  Translated  from  the  German  by  Charles 
Salter.  47  illustrations.  8vo.  cloth.  320  pp.  net,  $4.50 
—  Chemistry  of  Dyestuffs.  Translated  from  the  Sec- 
ond German  Edition  by  Charles  Salter.  8vo.  cloth. 
412  pp.  net,  $4.50 

WADMORE,  J.  M.  Elementary  Chemical  Theory.  Illus. 
i2mo.  cloth.  286pp.  net,  $1.50 

WALKER,  JAMES.  Organic  Chemistry  for  Students  of 
Medicine.  Illus.  6x9.  cloth.  328  pp.  net,  $2.50 

WANKLYN,  J.  A.  Milk  Analysis.  A  practical  treatise 
on  the  examination  of  milk  and  its  derivatives,  cream, 
butter  and  chee§e.  Illus.  I2mo.  cloth.  73  pp.  $1.00 
-  Water  Analysis.  A  practical  treatise  on  the  exami- 
nation of  potable  water.  Eleventh  Edition,  revised,  by 
W.  J.  Cooper.  Illus.  I2mo.  cloth.  213  pp.  $2.00 

WARNES,  A.  R.  Coal  Tar  Distillation  and  Working  Up 
of  Tar  Products.  67  illustrations.  5^x8^4.  cloth. 
197  pp.  net,  $2.50 

WILSON,  F.  J.,  and  HEILBRON,  I.  M.  Chemical  Theory 
and  Calculations.  An  elementary  text-book.  Illus.,  3 
folding  plates.  I2mo.  cloth.  145  pp.  net,  $1.00 

WINKLER,  C.,  and  LUNGE,  G.  Handbook  of  Technical 
Gas  Analysis.  Second  English  Edition.  Illustrated. 
8vo.  cloth.  190  pp.  $4.00 

WOOD,  J.  K.  The  Chemistry  of  Dyeing.  5x7^.  cloth. 
87  pp.  (Van  Nostrand's  Chemical  Monographs,  Xo. 
2.)  net,  $0.75 


iG  LIST  OF   CHEMICAL  BOOKS 

WORDEN,  E.  C.  The  Nitrocellulose  Industry.  A  com- 
pendium of  the  history,  chemistry,  manufacture,  com- 
mercial application,  and  analysis  of  nitrates,  acetates, 
and  xanthates  of  cellulose  as  applied  to  the  peaceful 
arts.  With  a  chapter  on  gun  cotton,  smokeless  pow- 
der and  explosive  cellulose  nitrates.  Illustrated. 
8vo.  cloth.  Two  volumes.  1239  PP-  ne*>  $10.00 

-Cellulose  Acetate.  A  monograph  of  the  history, 
chemistry,  manufacture,  technical  applications  and 
analysis  of  the  non-explosive  esters  of  cellulose  and 
starch.  Illus.  I2mo.  cloth.  In  Press. 

WREN,  HENRY.  Organometallic  Compounds  of  Zinc  and 
Magnesium.  5x7^.  cloth.  108  pp.  (Van  Nos- 
trand's  Chemical  Monographs,  No.  I.)  net,  $0.75 


Any  book  in  this  list  sent  postpaid  anywhere  in  the 
world  on  receipt  of  price. 

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